17th International Symposium on
Small Particles
and Inorganic Clusters
Program and Abstracts

7-12 September 2014,
Fukuoka, Japan

Edited by Atsushi Nakajima, Tatsuya Tsukuda, and Akira Terasaki.
© 2014 Local Organizing Committee for ISSPIC-17, JapanAll rights reserved. No part of this publication may be reproduced in any
form by print, photoprint, microfilm, electronic or any other means without
written permission of the publisher.

Preface
This book bundles program and abstracts for the 17th International
Symposium on Small Particles and Inorganic Clusters (ISSPIC-17) held in
Fukuoka, Japan, on 7-12 September 2014. The central subject of thesymposia is fundamental science of finite-size effects and control of material
properties at the nanometer scale.
The ISSPIC conference started as an international symposium on small
particles and inorganic clusters in 1976, and has since evolved into aninternational conference leading the cluster- and nano-science fields. The
symposia topics present a balanced overview of new results, emerging
trends and perspectives in the science of atomic and molecular clusters,
nanoparticles and nanostructures. The conference provides aninterdisciplinary forum for presentation and discussion of fundamental andtechnological developments in these fields. It is expected that theinterdisciplinary approach stimulates emergence of new research topics,
enabling innovative applications of nanoscience.
The ISSPIC-17 contents cover the areas of atomic and molecular clusters
and nanoparticles in various environments; free, supported, embedded,
ligated, assembled, etc. For these wide variety of clusters and nanoparticles,
the physical and chemical properties and functionalities have been
extensively investigated both by theoretical and by experimental approaches.
They include structure and thermodynamics, electronic structure andquantum effects, spectroscopy and dynamics, reactivity and catalysis,electron correlation for magnetism and superconductivity, optical properties
and plasmonics, carbon-based nanomaterials, biotechnological and medical
applications (imaging and sensors), environmental studies, device-oriented
topics, and energy-related topics.
The presentations, consisting of invited talks, hot topic oral contributions,and poster contributions, clearly show the width and breadth of the scientifictopics listed above, underlining that the field and scientific community of
ISSPIC is thriving, exciting, and challenging.
Finally, we would like to appreciate your continuous concern about theappalling disaster in the extremely destructive earthquake which hit thenortheastern area of Japan in March 2011. Your understandings andcontinuous supports have encouraged us to hold this ISSPIC-17 in Japan.
Atsushi Nakajima (chair) and Akira Terasaki (co-chair)
On behalf of the local organizing committee

International Advisory Committee
Julio A. Alonso
Vlasta Bonačić-Koutecký
Kit Bowen
Cathérine Bréchignac
Michel Broyer
A.W. Castleman, Jr.
Ori Chesnovsky
Ignacio L. Garzón
Hannu Häkkinen
Min HanUlrich Heiz
Claude Henry
Manfred Kappes
Uzi LandmanPeter Lievens
Karl-Heinz Meiwes-Broer
Paolo Milani
Atsushi Nakajima
Richard E. Palmer
Paul Scheier
Akira Terasaki
Tatsuya Tsukuda
Fabrice Vallée
Lai-Sheng Wang
Robert L. Whetten
Ludger Wöste

University of Valladolid, Spain
Humboldt University, Berlin, Germany
Johns Hopkins University, USA
CNRS, Orsay, France
Université Claude Bernard, Lyon, France
Pennsylvania State University, USA
Tel-Aviv University, Israel
Universidad Nacional Autónoma de México, Mexico
University of Jyväskylä, Finland
Nanjing University, China
Technische Universität Munich, Germany
University of Marseille, France
Karlsruhe Institute of Technology, Germany
Georgia Institute of Technology, Atlanta, USA
KU Leuven, Belgium
University of Rostock, Germany
University of Milano, Italy
Keio University, Japan
University of Birmingham, UK
University of Innsbruck, Austria
Kyushu University, Japan
University of Tokyo, Japan
Université Claude Bernard, Lyon, France
Brown University, Providence, USA
University of Texas in San Antonio, USAFree University Berlin, Germany

Emeritus members
R.S. BerryJ. Friedel
M.F. Gillet
Helmut Haberland
F. Hensel
Joshua Jortner
Koji KayaT. Patrick Martin
Rene Monot
Arne Rosen
Guanghou Wang

University of Chicago, USA
University Paris‐Sud, France
University Paul Cezanne, Aix Marseille, France
Albert‐Ludwigs University, Freiburg, Germany
Phillips University, Marburg, Germany
Tel Aviv University, Israel
RIKEN, Saitama, Japan
Max Planck Institute Stuttgart, Germany
Ecole Polytechnique Federale, Lausanne
University of Gothenburg, Sweden
Nanjing University, China

Local Organizing Committee
Atsushi Nakajima
Akira Terasaki
Shinji Hayashi
Hideo Higuchi
Koji Kaya
Yoshiyuki Kawazoe
Shigeo Maruyama
Hiroyuki Noji
Susumu Saito
Jun'ichi Sone
Testuya Taketsugu
Katsumi Tanigaki
Toshiharu Teranishi
Makoto Tokunaga
Masaharu Tsuji
Tatsuya Tsukuda

Keio University (Chair)
Kyushu University (Co-chair)
Kobe University
The University of Tokyo
RIKEN
Tohoku University
The University of Tokyo
The University of Tokyo
Tokyo Institute of Technology
National Institute for Materials Science
Hokkaido University
Tohoku University
Kyoto University
Kyushu University
Kyushu University
The University of Tokyo

Advisory Committee
Kazuhiko Ishihara
Toyoki Kunitake
Keiji Morokuma
Hisanori Shinohara
Toshio Yanagida

The University of Tokyo
Kitakyushu Foundation for the Advancement of Industry,
Science and Technology
Kyoto University & Emory University
Nagoya University
Osaka University & RIKEN

Local Steering Committee
Akira Terasaki
Masashi Arakawa
Kenji Furuya
Tamao Ishida
Haruyuki Nakano
Yasuro Niidome
Kazuhiko Ohashi
Takashi Ohshima
Kenji Sakota
Hiroshi Sekiya
Makoto Tokunaga
Masaharu Tsuji
Takeshi Tsuji
Sunao Yamada
Norio Yoshida
Kazunari Yoshizawa

Kyushu University (Chair)
Kyushu University
Kyushu University
Tokyo Metropolitan University
Kyushu University
Kagoshima University
Kyushu University
Kyushu University
Kyushu University
Kyushu University
Kyushu University
Kyushu University
Shimane University
Kyushu University
Kyushu University
Kyushu University

September 8th, Monday
9:00

Opening
Atsushi Nakajima / Sunao Yamada (Dean, School of Engineering, Kyushu University)
9:20
Resolving the atomic structure and meta-stability of size-selected gold clusters
Richard Palmer (Invited)
10:00 Quantum chemical molecular dynamics (QM/MD) simulations of nucleation, growthand healing processes of fullerenes, carbon nanotubes and graphenes
Keiji Morokuma (Invited)
10:40 Coffee break
11:10 Total structures of atomically precise gold nanoclusters and beyond
Rongchao Jin (Invited)
11:50 Nanoparticles by design: Fe75Pt72
Vijay Kumar
12:10 Gold-oxide nanoparticles - what is the oxidation state in gold?
Maxim Tchaplyguine
12:30 Lunch
14:00 Water clusters: thermal behavior and electron solvation
Bernd von Issendorff (Invited)
14:40 Nanoparticles and clusters from doped He nanodroplets
Paul Scheier (Invited)
15:20 Observation of phase transitions between finite temperature polymorphs of gallium
clusters: from β to γ to δ from first-principles
Nicola Gaston
15:40 Unusual temperature-dependent structure in the ionization yield of an aluminumcluster: possible superconducting electron pairing at T>100 K
Vitaly Kresin
16:00 Coffee break
16:30 Meteoric smoke nanoparticles and clouds in upper planetary atmospheres
Thomas Leisner (Invited)
17:10 Infrared photodissociation spectroscopy of carbon species of astrophysical relevanceE. Cristina Stanca-Kaposta
17:30 Vibrational and low-temperature thermal properties of metal nanoparticles
Ignacio L. Garzón
17:50 Industry (National Instruments Japan and TOYAMA Co., Ltd.)
18:30

Monday September 8th

INV1

Resolving the atomic structure and meta-stability of size-selected gold clusters
Richard E Palmer
Nanoscale Physics Research Laboratory, University of Birmingham, U.K.
r.e.palmer@bham.ac.uk; www.nprl.bham.ac.uk

The controlled deposition of size-selected nanoclusters, assembled from atoms in the gas phase,is a novel [1] but increasingly popular route to the fabrication of functional surfaces structured on
the sub-10nm scale, with applications in catalysis, coatings, biochips [2], etc. Efforts to scale-up
the rate of cluster generation thus promise significant future impact. However fundamental
questions remain over the equilibrium atomic structures of the clusters themselves, since direct
gas phase structural studies have been limited and new techniques like aberration-correctedscanning transmission electron microscopy (ac-STEM) are only now being applied to soft-landed,size-selected clusters. I will survey our recently published [2-6] and latest systematic ac-STEM
experiments which address the atomic structure of size-selected “magic number” gold clusters Au20, Au55, Au309, Au561, and Au923 – including dynamical manipulation experiments [6], whichprobe the transformation of metastable isomers into more stable configurations, and reactionexposure experiments, which probe the stability of the cluster structures under real catalytic
conditions. The results distinguish the predominant, competing isomers as a function of cluster
size, expose concepts such as templated-growth, provide a body of date to stimulate andconstrain computational models and are readily extendable to other sizes and cluster materials
including binary systems.
Reference(s)[1] R.E. Palmer, S. Pratontep and H.-G. Boyen, Nature Materials 2 443 (2003).
[2] R.E. Palmer and C. Leung, Trends in Biotechnology 25 48 (2007).
[3] Z.W. Wang and R.E. Palmer, Nano Lett. 12 91 (2012).
[4] Z.W. Wang and R.E. Palmer, Nanoscale 4 4947 (2012) [Cover].
[5] Z.W. Wang and R.E. Palmer, Nano Lett. 12 5510 (2012).
[6] Z.W. Wang and R.E. Palmer, Phys. Rev. Lett. 108 245502 (2012).

Monday September 8th

INV2

Quantum chemical molecular dynamics (QM/MD) simulations of nucleation,
growth and healing processes of fullerenes, carbon nanotubes and graphenes
Keiji Morokuma
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan
Nucleation, growth and healing of carbon nanostructures (fullerenes, carbon nanotubes andgraphenes, respectively, without catalyst, with metal cluster catalysts and on metal surfaces) are
self-assembly processes from a chaotic pool of small carbon clusters to ordered nanostructures.
Although some “theories” exist that advocate well-defined pathways for construction of orderedstructures, high-temperature nature of these processes strongly suggests that the dynamics is thekey.
In order to explicitly consider the quantum nature of these sp2 carbon systems and follow
dynamics for up to nano second, we have been using quantum chemical molecular dynamics(QM/MD) simulation techniques with a semi-empirical density functional tight-binding theory called
DFTB. For all these fullerenes (0 dimensional or 0D), carbon nanotubes (1D) and graphenes (2D),
the self-assembly process takes place in a surprising similar fashion. At first, small carbon species(such as C2 and C4) assembles in chains, and a Y-shaped carbon chain junction closes and forms
the first ring that is always five-membered. “Nucleation”, formation of several five andsix-membered aromatic rings takes places by entanglement of carbon chains around thisfive-membered ring. The “growth” of sp2 carbon network is continued by addition of more carbon
species into the system. The growth produces five-membered as well as six-membered rings andthus the chirality of growing structures is not maintained. During the growth process, a slow
healing process takes place at the same time. In the healing process defects consisting mainly of
five- (and seven-) membered rings are converted via a variety of processes (such as addition of
one carbon atom) into six-membered rings. Usually the chirality of the original cap of the nanotube
is lost during the growth process and the healing does not restore the original chirality. Dependingon the support that retains an open end of growing structure, different products are obtained;
without support, all open ends close to form a fullerene structure; with metal cluster support, the1D nano tube is formed; and with metal surface support, the 2D graphene is formed. The lecture
will illustrate examples and principles of these carbon nanostructure self-assembly.
Reference(s)[1] S. Irle, A. J. Page, B. Saha, Y. Wang, K. R. S. Chandrakumar, Y. Nishimoto, H.-J. Qian, K.
Morokuma, in eds. J. Leszczynski and M. Shukla, “Practical Aspects of Computational
Chemistry: An Overview of the Last Two Decades and Current Trends”, 103-172 (2012):
Springer-European Academy of Sciences. ISBN 978-94-007-0922-5[2] A. J. Page, F. Ding, S. Irle and K. Morokuma, Rep. Prog. Phys. In press.
[3] H-B. Li, A. J. Page, C. Hettich, B. Aradi, C. Köhler, T. Frauenheim,.S. Irle and K. Morokuma,
Chem. Sci. doi:10.1039/c4sc00491d

Monday September 8th

INV3

Total Structures of Atomically Precise Gold Nanoclusters and Beyond
Rongchao Jin
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA
Determining the total structures of nanoclusters constitutes a major goal in nanoscience research.
Gold nanoclusters are particularly attractive due to their extraordinary stability and elegant opticalproperties. A prerequisite to total structure determination is to obtain atomically precise
nanoclusters, which had been a major challenge in the past research and thus hampered the
pursuit of fundamental science of nanoclusters. We have recently developed successful
methodologies for synthesizing a series of atomically precise gold nanoclusters protected bythiolates (denoted as Aun(SR)m, with n ranging from a few dozens to several hundreds). Suchultrasmall particles (ca. 13 nm) exhibit distinct quantum size effects and interesting
electronic/optical properties, which are fundamentally different from the properties of larger
counterpartsplasmonic nanoparticles. New types of atom-packing structures have been
discovered in Aun(SR)m nanoclusters through X-ray crystallographic analysis. These well-defined
nanoclusters hold potential in catalysis as new model catalysts, and atomic levelstructure-reactivity correlation will ultimately offer fundamental understanding on nanocatalysis.
References[1] H. Qian, M. Zhu, Z. Wu, and R. Jin, Acc. Chem. Res. 45 (2012) 1470.
[2] C. Zeng, T. Li, A. Das, N. L. Rosi, and R. Jin, J. Am. Chem. Soc. 135 (2013) 10011.
[3] C. Zeng, Y. Chen, G. Li, and R. Jin, Chem. Mater. 26 (2014) 2635.
[4] H. Kawasaki, S. Kumar, G. Li, C. Zeng, D. R. Kauffman, J. Yoshimoto, Y. Iwasaki, and R. Jin,
Chem. Mater. 26 (2014) 2777.
[5] G. Li, C. Zeng, and R. Jin, J. Am. Chem. Soc. 136 (2014) 3673.
[6] A. Das, T. Li, K. Nobusada, C. Zeng, N. L. Rosi, and R. Jin, J. Am. Chem. Soc. 135 (2013)
18264.
[7] H. Qian, D.-e. Jiang, G. Li, C. Gayathri, A. Das, R. R. Gil, and R. Jin, J. Am. Chem. Soc. 134(2012) 16159.
[8] D. R. Kauffman, D. Alfonso, C. Matranga, H. Qian, and R. Jin, J. Am. Chem. Soc. 134 (2012)
10237.
[9] G. Li and R. Jin, Acc. Chem. Res. 46 (2013) 1749.

Monday September 8th

HT1

Nanoparticles by Design: Fe75Pt72
Bheema Lingam Chittari1 and Vijay Kumar,1,2
1

Dr. Vijay Kumar Foundation(VKF), 1969 Sector 4, Gurgaon 122001, Haryana, India

2

Center for Informatics, School of Natural Sciences, Shiv Nadar University, Chithera, Gautam
Budh Nagar - 203207, U.P., India

The development of size specific nanoparticles of materials is important for their applications totake advantage of their specific properties. Core-shell nanoparticles of a variety of materials havebeen studied. In particular Pt nanoparticles with a core of another transition metal have beenfound to improve dramatically their catalytic activity. Moreover, FePt nanoparticles are importantfor high density magnetic recording as well as for the development of strong magnets together
with soft magnets. We have systematically investigated Fe-Pt nanoparticles of different sizes andwith different initial structures including bulk fragments, decahedral, and icosahedral structures. In
one such study it is found that a bulk fragment of Fe51Pt12 instantaneously transforms to
icosahedral structure with a few Pt atoms inside and eight atoms attached to icosahedral structureon the surface. We removed the eight atoms on the surface and subsequently moved the Pt atoms
from inside to the surface. This lowered the energy of the 55-atom nanoparticle suggesting
segregation of Pt to be favorable on the surface. Also it indicates that at this size range theicosahedral structure is preferred. Further calculations on several compositions of small size
nanoalloys showed Fe-Pt ordering or maximizing the unlike bonds to be most favorable. Using
these considerations we found a unique combination of 147 atom icosahedral Fe-Pt nanoparticle
in which 55 atom core is made of Fe atoms and 72 Pt atoms are on the outer shell of Maykay
icosahedron. 20 Fe atoms are on the centers of the Pt hexagons giving the stoichiometry Fe75Pt72.
This has 231 µB magnetic moments. In this structure the magnetic moments on Fe and Pt atoms
are higher compared with the values in bulk FePt. Note that Fe55 cluster has icosahedral structure
to be most favorable with large magnetic moments. Also Pt likes to segregate at surface, and thereis ordering of FePt on the surface which leads to this optimal nanoparticle. This is the finest model
nanoparticle by design for magnetic as well as catalytic applications. The overall composition ofthis nanoparticle is FePt- like, but it decomposes in to a Fe core and Fe-Pt shell. We hope thatsuch structures are likely to exist for even bigger nanoparticles before a transition to Fe-Pt likecore. We anticipate that our studies will motivate experiments on synthesis of such nanoparticles
for catalysis, ultrahigh density magnetic recording applications as well as for building strong
magnets without using rare earths.

Monday September 8th

HT2

Gold-oxide nanoparticles – what is the oxidation state in gold?
M.Tchaplyguine1, M.H.-Mikkelä1, Ch. Zhang2, T. Andersson2, O. Björneholm2
1MAX-lab, Lund University, P.O. Box 118, 22100 Lund, Sweden

2

Department of Physics and Astronomy, Uppsala University, Box 530, 75121 Uppsala, Sweden

Over the years it has been vividly discussed what made gold nanoparticles so drastically different
to “bulk” gold in chemical activity- their size, their peculiar electronic structure, their interaction witha specific substrate, etc. [1,2,3,4]. The chemical reaction discussed most is the oxidation of carbon
monoxide at gold surface in the presence of oxygen. This reaction proceeds via the formation of
the surface oxide of the catalyst – gold.

Among the main experimental obstacles to ourunderstanding of gold reactivity enhancement in nanoparticles are the difficulty to oxidize gold atlaboratory conditions and the instability of gold oxide. Using photoelectron spectroscopy thechemical state of gold in the oxide at “macroscale” has been established to be typically trivalent(Au2O3): Photoelectron spectroscopy detects well-separated responses of the oxide and metallic
gold in the Au 4f-region spectrum, the oxide being 1.9 eV higher in electron binding energy than
the signal from metallic gold. In the present work gold-oxide containing nanoparticles have been
fabricated in the size regime known to be efficient for catalytic oxidation – below 10 nm. Ourfabrication method is based on vapour aggregation, involving metal atoms sputtered off the solid in the oxygen-containing magnetron-discharge plasma. The gold oxidation state/valency has been
investigated by means of x-ray photoelectron spectroscopy- “on the fly” for the particles in the
beam and after the deposition on SiO2 substrate. In both cases the gold-oxide response occurs tobe 1.5 eV above the metallic response what corresponds to lower oxidation states with valency+2 or +1 – in contrast to characteristic for the “bulk” value +3. Some earlier results suggest theformation of divalent gold oxide at our conditions. The gold valency in an oxide comes into the playwhen its interaction with CO molecules is about to take place. A CO molecule is a two-electron
donor in a reaction with noble metals. If the substance to which CO has to bind is a divalent metalcompound with dangling bonds at the surface the situation is optimal for the CO chemisorption.
Our approach allowing to fabricate nanoparticles with lower gold oxides and to derive theiroxidation degree may be relevant for the studies connected to nano-catalysis. Moreover, taking
into account our recent results on silver-oxide containing nanoparticles [5], it may be seen as amethod of producing catalytically active nanostructured systems with controlled properties.
References[1] D. Widmann, R. J. Behm. Acc. Chem. Res. 47 (2014) 740.
[2] H. Häkkinen, M. Moseler, U. Landman, Phys. Rev. Lett. 89 (2002) 033401.
[3] B. Yoon, H. Häkkinen, U. Landman, et al, Science 307 (2005) 403.
[4] M.Haruta. Cat.Today 36 (1997) 153.
[5] M.Tchaplyguine, Ch.Zhang, T.Andersson, O.Björneholm. ChemPhys.Lett. 600 (2014) 96

Monday September 8th

INV4

Water clusters: thermal behavior and electron solvation
Bernd v. Issendorff

Physikalisches Institut, Universität Freiburg, 79104 Freiburg, Germany

Bulk water exhibits many unusual properties, which mirror the complexity of its hydrogen network
structure. It is therefore not surprising that water clusters and nanoparticles are special in many
aspects as well. We have recently shown that negatively charged water clusters exhibit a meltinglike transition at surprisingly low temperatures (at about 120 K for H20118-) [1] . Further studies
have shown that this behavior depends only weakly on the charge state of the cluster or on thetype of impurity incorporated. Furthermore the size dependence indicates that the transition does
not extrapolate to the melting transition of normal ice, but rather to the glass transition of
amorphous ice, which occurs at about 136 K. This can be rationalized by the fact that water
clusters with few hundred molecules do not form a crystalline network like bulk ice, but exhibit
structures much closer to that of the amorphous forms of solid water.
Another phenomenon closely related to the hydrogen network structure of water is the solvationof a free electron. Since the first observation of negatively charged water clusters [2] the question
has been discussed at what size the attached electron gets truly solvated, that is resides inside
the cluster. We could recently show that apart from the already known three isomer classes ofwater cluster anions (in all of which the electron is bound to the cluster surface), another isomerclass exists, which becomes dominant at about size 46 and most probably is the one with aninternal electron [3]. Extending the photoelectron spectroscopy studies to cluster anions with up
to 1600 water molecules we could now obtain a reliable extrapolation of the electron binding
energy for the bulk. This yields a value of about 3.6 eV, which is slightly larger than commonly
assumed.

Reference(s)[1] C. Hock, M. Schmidt, R. Kuhnen, C. Bartels, L. Ma, H. Haberland, and B. v.Issendorff, Phys.
Rev. Lett. 103, 073401 (2009).
[2] M. Armbruster, H. Haberland, and H.-G. Schindler, Phys. Rev. Lett. 47, 323 (1981).
[3] L. Ma, K. Majer, F. Chirot, and B. v. Issendorff, J. Chem. Phys. 131, 144303 (2009).

Monday September 8th

INV5

Nanoparticles and clusters from doped He nanodroplets
Michael Renzler1, Johannes Postler1, Alexander Kaiser1, Matthias Daxner1, Diethard K. Böhme2,David Stock1, Martin Kuhn1, Stefan Ralser1, Stephan Denifl1, Olof Echt2 and Paul Scheier1
1Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Austria
2

3

Department of Chemistry,York University, Toronto, ON, Canada M3J 1P3

Department of Physics, University of New Hampshire, Durham, NH 03824, United States

Pickup of atoms and molecules into superfluid He nanodroplets (HND) is a powerful technique toform clusters and nanoparticles at low (0.38K) temperatures. The resulting dopant complexes aremostly analyzed utilizing mass spectrometry after ionization [1,2]. In the present contribution theinfluence of charge on the physisorption of CO2 on fullerenes is investigated. The linear shape of
CO2 molecule and its response to a positive surface charge, due to the slightly negative terminal O
atoms, can lead to “packing” consequences and increased surface adsorption.
Recently several groups deposited neutral metal and semiconductor nanoparticles grown in large
HND and analyzed them by transmission electron microscopy [3-5]. Both spherical nanoparticles
and nanometer wide fibers have been reported. However, the typical log-normal size distributionof the neutral HND and the Poissonian pickup statistics leads to a substantial size spread of thedopant clusters. Here we report on a novel approach that reduces the size distribution of the HND,
simply by ionization. The yield of the resulting singly charged HND is very high and enables theefficient formation of mono-dispersed clusters via subsequent pickup.
This work was supported by the FWF, Wien (P23657, I978 and P26635)
Reference(s)[1] J.P. Toennies, and A.F. Vilesov, Angew. Chemie Int. Ed. 43 (2004) 2622-2648.
[2] O. Echt, A. Kaiser, S. Zöttl, A. Mauracher, S. Denifl, P. Scheier, ChemPlusChem 78 (2013)
910-920[3] L. Gomez, E. Loginov, and A.F. Vilesov, Phys. Rev. Lett. 108 (2012) 155302.
[4] A. Volk, P. Thaler, M. Koch, E. Fisslthaler, W. Grogger, and W.E. Ernst, J. Chem. Phys. 138(2013) 214312.
[5] SF. Yang, A.M. Ellis, D. Spence, C. Feng, A. Boatwright, E. Latimer, and C. Binns, Nanoscale 5(2013) 11545-11553

Monday September 8th

HT3

Observation of phase transitions between finite temperature polymorphs ofgallium clusters: from β to γ to δ from first-principles
N. Gaston1, K. G. Steenbergen2
1

MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical andPhysical Sciences, Victoria University of Wellington, New Zealand2

Department of Chemistry, The University of Kansas, USA

Gallium is a highly polymorphic element with a rich phase diagram, which poses a real challenge
to first-principles theory.

The experimental discovery of superheating in gallium clusters [1]contradicted the clear and well-demonstrated paradigm that the melting temperature of a particle
should decrease with its size [2]. In addition, the extremely sensitive dependence of melting
temperature on size also goes to the heart of nanoscience, and the interplay between the effects
of electronic and geometric structure.
We have performed extensive first-principles molecular dynamics calculations, incorporating
parallel tempering for an efficient exploration of configurational phase space [3].

In thenanoparticles, melting is preceded by transitions between phases. A structural feature is identified
that systematically increases with the latent heat and appears throughout the observed phasechanges of this curious metal. We will present our detailed analysis of the solid-state isomers,
performed using extensive statistical sampling of the trajectory data for the assignment of cluster
structures to known phases of gallium [4].
Finally, we offer a first explanation of the greater-than-bulk melting temperatures, through analysisof the factors that stabilise the liquid structures.
Reference(s)[1] G. A. Breaux, R. C. Benirschke, T. Sugai, B. S. Kinnear, and M. F. Jarrold,
Phys. Rev. Lett. 91, 215508 (2003)[2] P. Pawlow, Z. Phys. Chem. 65, 1 (1909)[3] K.G. Steenbergen, N. Gaston, Physical Review B 88, 161402 (2013)[4] K.G. Steenbergen, N. Gaston, J. Chem. Phys., 140, 064102 (2014)

Monday September 8TH

HT4

Unusual temperature-dependent structure in the ionization yield of analuminum cluster: Possible superconducting electron pairing at T>100 K
Avik Halder, Anthony Liang, and Vitaly V. Kresin
Department of Physics and Astronomy, University of Southern California, Los Angeles, CA
A number of theoretical papers (see, e.g., [1-4]) have predicted that free metal clusters with shellstructure exhibit superconducting-type electron pairing.

This should occur only for certain

individual sizes and materials, but when it does, it is expected to be greatly enhanced relative tobulk samples, with a corresponding increase in the critical temperature.

This is a uniqueconsequence of the high electron state degeneracy associated with shell structure.
Superconducting pair correlations should have spectroscopic manifestations. To search for the
first observation of such an effect, we have carried out a series of accurate measurements of thephotoionization yield curves of Aln clusters for several temperatures in the range of 70 K – 230 K.
The clusters’ internal temperatures were controlled by a newly designed thermalizing tube
attached to a magnetron-sputtering condensation cluster source.
The experiment revealed that while the majority of yield curves show no significant temperature
variation, a few clusters are exceptional: a noticeable feature appears in the near-thresholdregion and grows substantially as the temperature decreases to ≈100 K. For example, this is
prominent in the closed-shell cluster Al66 (198 valence electrons), which had in fact been identified
by theory as one of the candidates for high-Tc pairing. This behavior has not been reported forcluster previously, but is reminiscent of temperature effects in threshold photoemission fromhigh-Tc superconductors [5]. It is a consequence of the increase in the effective density of states
due to electron pairing. We suggest that the data represent a signature of superconducting
transition in a “magic” metal cluster with Tc >100 K.
This work is supported by the U.S. National Science Foundation.
dY/dE (Y=ionization yield)

Relative height of near-threshold peak as a function of temperature

Reference(s)[1] V. Z. Kresin, and Yu. N. Ovchinnikov, Phys. Rev. B 74, 024514 (2006).
[2] M. Groitory et al., Phys. Rev. B 83, 214509 (2011).
[3] Z. Lindenfeld et al., Phys. Rev. B 84 064532 (2011).
[4] M. Hopjan and P. Lipavský, Phys. Rev. B 89, 094507 (2014).
[5] S. A. Nepijko et al., Physica C 288, 173 (1997).

Monday September 8th

INV6

Meteoric smoke nanoparticles and clouds in upper planetary atmospheres
Denis Duft1, Mario Nachbar2, Jan Meinen1, Markus Eritt2 and Thomas Leisner1,21Institute for Meteorology and Climate Research, Karlsruhe Institute of Technology, Karlsruhe,
Germany2

Institut für Umweltphysik, University of Heidelberg, Heidelberg, Germany

Most planets, including the earth feature a pronounced global minimum of temperature at themesopause, i.e. at the transition into the thermosphere. This region is prone to form clouds
whenever condensable gases exist in the atmosphere. These outermost cloud layers may
determine largely the planetary appearance to remote sensing instruments.
On earth, these clouds are ubiquitous in the polar summer mesopause and are known asnoctilucent clouds. As the mesopause is generally far above the ground (on the earth ~85 km), thecloud condensation nuclei are not primary aerosol particles that are transported up from ground,but are constituted by nanoparticles formed by the recondensation of meteoric material. These are
the only type of aerosol in the atmosphhere that remain of nanometer- size due to the lowtemperature and pressure in the mesosphere.
Fig.1 Scheme ofthe experimental
setup for heterogeneous chemistryon atmosphericnanoparticles.
“TRAPS”:
TrappedReactive
AtmosphericParticles
SpectrometerIn this contribution, we present a novel laboratory experiment TRAPS (Fig.1) that allows to
prepare and analyze meteoric dust nanoparticles in an electrodynamic trap under conditions ofplanetary mesospheres [1]. We present first results of the nucleation and growth of ice on theseparticles and compare the results to classical nucleation theory.
Reference(s)[1] Meinen, J., Khasminskaya, S., Ruehl, E., Baumann, W. and Leisner, T. (2010), Aerosol
Science and Technology 44(4): 316-328.

Monday September 8th

HT5

Infrared Photodissociation Spectroscopy of Carbon Species of AstrophysicalRelevance
E. Cristina Stanca-Kaposta,1 Falko Schwaneberg,1 Xiaowei Song,2 Matthieu Lalanne,1 Matias R.
Fagiani,2 Ludger Wöste1 and Knut R. Asmis2,3
1

Institut für Experimentalphysik, Freie Universität Berlin, Germany

2

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
3

Wilhelm-Ostwald-Institut, Universität Leipzig, Germany

It is well known that the interstellar medium is rich in different carbon species including long linear
carbon chains, polyacetylanic radicals as well as more complex systems such as C2H5OCHO andC3H7CN. [1] Besides neutral and cationic molecules, more recently and unexpectedly, molecularanions like C2nH¯ (n = 2 - 4) as well as C3N¯ and C5N¯ have been detected and identified basedon comparison with laboratory experiments.
Here, we present the gas phase vibrational spectroscopy of cryogenically-cooled carbon anion
species of the type CnN¯, CnH¯ and CnO¯ by way of infrared photodissociation (IRPD)
spectroscopy of messenger-tagged CnM‾∙m(D2) (M = N, H ,O) complexes.[2] The experiments are
performed in a tandem mass spectrometer consisting of a quadrupole mass filter, a temperatureadjustable (8 - 350K) linear ring-electrode radio-frequency ion trap and a linear time-of-flight (TOF)
mass filter. The anions of interest are generated by reactive sputtering of a graphite target within amagnetron sputter source. CnM‾∙m(D2) (M = N, H ,O) complexes are formed via three-bodycollisions in the ion trap which is held at 15-20 K and is filled with D2 as buffer gas. Irradiation of
the anions with a tunable infrared OPO/OPA laser occurs in the center of the extraction region of
the TOF mass filter. The vibrational action spectra are measured by monitoring theIR-photoinduced loss of D2 molecules from the CnM‾∙m(D2) complexes as a function of photon
energy.
The IRPD spectra are assigned based on a comparison to ab initio [3] and DFT vibrationalfrequencies and intensities. Experimentally measured vibrational transitions are in good
agreement with the predicted anharmonic as well as, where not available, scaled harmonicfrequencies. The influence of the D2-messenger molecules on the structure and the IRPD
spectrum is found to be small. Compared to the results of previous IR matrix isolation studies
additional, in particular weaker, IR-active transitions are identified.
References[1] Ramya Nagarajan and John P. Maier, Int. Rev. Phys. Chem. 29 (2010) 521[2] E. Cristina Stanca-Kaposta, Falko Schwaneberg, Matias R. Fagiani, Torsten Wende, Franz
Hagemann, Annett Wünschmann, Ludger Wöste, and Knut R. Asmis, Z. Phys. Chem 228(2014) 351.
[3] P. Botschwina and R. Oswald, J. Chem. Phys. 129 (2008) 044305.

Monday September 8th

HT6

Vibrational and Low-Temperature Thermal Properties of Metal Nanoparticles
Huziel E. Sauceda,1 J. Jesús Pelayo,1 Fernando Salazar,2 Luis A. Pérez,1 Ignacio L. Garzón1
1

Universidad Nacional Autónoma de México, Instituto de Física, 01000 México, D. F., México
2

Instituto Politécnico Nacional, ESIME Culhuacán, 04430 México, D. F., México

We report the vibrational spectra and density of states of Au, Pt, and Ag nanoparticles in the size
range of 0.5 - 4 nm. The vibrational spectra were calculated through atomistic simulations using
the many-body Gupta potential. Linear relations with the nanoparticle diameter were obtained forthe periods of two characteristic oscillations: the quasi-breathing and the lowest frequency(acoustic gap) modes. These results are consistent with the calculation of the periods
corresponding to the breathing and acoustic gap modes of an isotropic, homogeneous metallic
nanosphere, performed with continuous elastic theory using bulk properties. Additionally,
experimental results on the period of isotropic volume oscillations of Au nanoparticles measured
by time-resolved pump-probe spectroscopy are presented, indicating a linear variation with themean diameter in the size range of 2 - 4 nm. These, and similar results previously obtained for Pt
nanoparticles with size between 1.3 – 3 nm, are in good agreement with the calculatedquasi-breathing mode periods of the metal nanoparticles, independently of their morphologies. [1]We also report the vibrational spectrum and density of states (VDOS) of the cationic sodium
cluster Na139+ using DFT. The calculated vibrational frequencies were used to evaluate the cluster
caloric curve and heat capacity at low temperatures. An excellent agreement was obtained
between the calculated caloric curve and experimental data recently reported down to 6 K. A
further analysis shows that the calculated heat capacity of the 139-atom cationic sodium cluster
does not follow the bulk Debye T3 law at very low temperatures, due to the discreteness of thecluster frequency spectrum, and to the finite value of its acoustic gap (lowest frequency value). [2]The size and shape dependence of the specific heat at low temperatures as well as its evolution
towards the bulk limit for Au nanoparticles in the size range of 0.5-4 nm is also reported. The
results indicate that the acoustic gap is responsible of a slight reduction in the specific heat withrespect to bulk in the temperature range, 0 < T <Tr , (Tr ≈ 5 K for Au nanoparticles with size 1.4nm). [3] Also, the well-known increment in the specific heat of metal nanoparticles with respect tothe bulk value, caused by the enhancement of the VDOS at low frequencies, is recovered for Tr <T < Ts (Ts ≈ 35–45 K). [3]Reference(s)[1] H. E. Sauceda, D. Mongin, P. Maioli, A. Crut, M. Pellarin, N. del Fatti, F. Vallée,
and I. L. Garzón, J. Phys. Chem. C 116 (2012) 25147.
[2] H. E. Sauceda, J. J. Pelayo, F. Salazar, L. A. Pérez, and I. L. Garzón,
J. Phys. Chem. C 117 (2013) 11393.
[3] H. E. Sauceda, F. Salazar, L. A. Pérez, and I. L. Garzón, J. Phys. Chem. C 117 (2013) 25160.

September 9th, Tuesday
9:00

Cluster assemblies as novel nanoscale materials with tunable properties
Shiv Khanna (Invited)
9:40
Mass spectrometric investigations of nanoparticles: from small liganded metal
nanoclusters to large nanoparticles assemblies
Rodolphe Antoine (Invited)
10:20 Far-infrared spectroscopy of clusters of the platinum metals: evidence for cubic
structures of Ru and Ir clusters
André Fielicke
10:40 Conference photo
Coffee break
11:10 Professor Satoru Sugano Memorial
11:30 Energetics, edge geometries, and electronic properties of silicene
Susumu Saito
11:50 One-dimensional uneven structured exotic-nanocarbon: geometric curvature effects
at nanoscale
Jun Onoe
12:10 The formation of supported carbon clusters during graphene chemical vapor
deposition (CVD) growthFeng Ding
12:30 Lunch
14:00 Effects of electronic and geometric structure on the activity of size-selected model
catalysts and electrocatalysts
Scott Anderson (Invited)
14:40 Plasmonic property of multidimensional self-assembled metallic nanoparticles
Kaoru Tamada (Invited)
15:20 Surface plasmons in quantum-sized noble-metal clusters: quantum calculations andthe classical picture of charge oscillations
Hans-Christian Weissker
15:40 Clusters for photocatalysis
Gunther Andersson
16:00 Coffee break
16:30 Poster Session A
18:30 Cultural event

Tuesday September 9th

INV7

Cluster Assemblies As Novel Nanoscale Materials With Tunable Properties
S. N. Khanna
Department of Physics, Virginia Commonwealth University, Richmond, VA 23284-2000, USA
An exciting development in nanoscience is the formation of materials whereby atomic clusters
serve as the building blocks. Since the properties of clusters change with size, composition andthe charged state, cluster assemblies offer the attractive proposition of forming materials withnovel combination of properties. Cluster solids can be stabilized either by using counter ions or via
ligands to passivate the reacting species. The resulting assemblies allow the integration ofmultiple length scales into a hierarchical material and the emergent properties depend on thenature of the building blocks as well as the architecture of the assembled material as the solids
combine intra-cluster, inter-cluster, linker-cluster, and ligand-cluster interactions, unavailable inconventional atomic solids.
The talk will first review our efforts in synthesizing cluster-based solids where the primitive motifs
are the multiply-charged polyatomic anions, called Zintl anions. New building blocks can beformed by covalently linking multiple anions and the nature of the assemblies can be further
controlled by extending the countercations to include cryptated ions. Through variations of theanionic motifs and alkali/cryptated ions, it becomes possible to assemble the resulting solids invarious architectures including zero, one, two, and three dimensional solids. In particular, I will
present our results on the cluster-assembled materials derived from anionic As73 combined withcountercations including alkali metals and cryptated K ions, and building motifs that also involve
Zintl ions covalently linked with Hg, Zn, Cd, Pd, etc. The talk will highlight how different cluster
assemblies can be synthesized by using covalent linkers and assembling them withcountercations in various proportions. The talk will also review two recent developments. The first
involves ligated cluster assemblies involving metallic cores. In particular, I will present our resultson assemblies with a bi-metallic core and the properties of the resulting material. The second
involves our effort in developing air stable nano-materials. I will describe our recent success insynthesizing and characterizing new alkaline earth Metal Organic-Frameworks (MOFs). Taking
the band gap energy of the resulting material as the property of choice, I will show that the energy
bands in these cluster solids exhibit far less dispersion than in atomic solids and that the band gap
energy can be controlled over a wide range.
The talk will also review our recent efforts in designing novel rare earth free magnets that could
rival the current rare earth based permanent magnets. I will show that the materials consist of
nanoparticles with ultra high magnetic anisotropies offering potential for memory storage and otherapplications.

Tuesday September 9th

INV8

Mass Spectrometric Investigations of Nanoparticles : from small liganded metal
nanoclusters to large nanoparticles assemblies
Rodolphe Antoine
Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS,Université de Lyon 69622
Villeurbanne cedex, France
Metal nanoparticles (NPs) are fascinating due to their unique optical and electronic properties,
which are size and structure dependent. The recent progress in the synthesis of functionalizedNPs (in particular with biomolecules) challenges the understanding of their electronic,
spectroscopic, and chemical properties at the molecular level. Gas phase studies offer theopportunity to produce and study hybrid systems under well-defined conditions.
The present work aims at characterizing nanoparticles with mass spectrometric investigations. In afirst part of my presentation, I will present results on structural and optical characterization of small
protected metal clusters by high-resolution mass spectrometry and coupling with action
spectroscopy.[1, 2] Then I will move to a new instrumental set-up to study large nanoparticles in
the gas phase, by determining accurately their mass and charge.[3] A charge detection mass
spectrometry technique combined to ESI technique is used to “weighing” large DNAs,
nanoparticles and nanoparticles assemblies in the megadalton range of molecular weight. I willshow how the simultaneous measure of mass and charge can be used to fathom structuralproperties of nanoparticles assemblies. I will also present the implementation of tandem mass
spectrometry for experiments on single nanoobjects, using two charge detection devices. Single
ions can be stored for several dozen milliseconds. During the trapping time, single ions can be
irradiated by a continuous wavelength CO2 laser. Illustration of infrared multiphoton dissociation
tandem mass spectrometry will be given for single megadalton ions of DNAs.[4, 5]
References[1] R. Hamouda, B. Bellina, F. Bertorelle, I. Compagnon, R. Antoine, M. Broyer, D. Rayane, P.
Dugourd, Journal of Physical Chemistry Letters, 1 (2010) 3189-3194.
[2] F. Bertorelle, R. Hamouda, D. Rayane, M. Broyer, R. Antoine, P. Dugourd, L. Gell, A. Kulesza,
R. Mitric, V. Bonacic-Koutecky, Nanoscale, 5 (2013) 5637-5643.
[3] T. Doussineau, C.Y. Bao, C. Clavier, X. Dagany, M. Kerleroux, R. Antoine, P. Dugourd, Review
of Scientific Instruments, 82 (2011) 084104.
[4] R. Antoine, T. Doussineau, P. Dugourd, F. Calvo, Physical Review A, 87 (2013) 013435.
[5] T. Doussineau, R. Antoine, M. Santacreu, P. Dugourd, Journal of Physical Chemistry Letters, 3(2012) 2141-2145.

Tuesday September 9th

HT7

Far-infrared spectroscopy of clusters of the platinum metals:
Evidence for cubic structures of Ru and Ir clusters
Christian Kerpal,1 Jonathan T. Lyon,2 John Bowlan,1 Dan J. Harding,1 and André Fielicke1,3
1
2

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany

Department of Natural Sciences, Clayton State University, Morrow, Georgia, United States
3

Institut für Optik und Atomare Physik, Technische Universität Berlin, Germany

Transition metal clusters are frequently used as model systems for low coordinated sites ofextended surfaces and their study can provide valuable insights into the mechanisms of surface
reactions. In many cases, however, there is a lack of information on their structures and therelationship between structure and chemical behavior. Present developments of computational
electronic structure methods often still have difficulties with a reliable prediction of cluster
structures, and their properties, from first principles. This holds in particular for metals with only
partially filled d (transition metals) or f (lanthanides, actinides) shells or for heavy elements, likegold, where relativistic effects become more pronounced. Experimental data can help for testing
the validity of these predictions and in motivating methodological developments. Cluster size
specific far-infrared spectra as obtained via infrared multiple photon dissociation of messenger
complex are structural fingerprints and allow via comparison to spectra predicted, i.e. from DFT
calculations, for structural assignments.
Clusters of the platinum group metals (4d: Ru, Rh, Pd; 5d: Os, Ir, Pt) are of particular interest [1],due to the importance of the metals in catalytic applications, but also due to the surprisingprediction of uncommon simple cubic structural motifs [2,3]. However, for Rh the stability of cubic
geometries seems to be an artifact of the GGA-DFT method and experimentally polytetrahedral
structures are identified that are also found as most stable isomers when using hybrid functionals
in DFT [4]. While also Pt clusters show polytetrahedral structures similar to many other transition
metals [5], Ru and Ir indeed appear to follow the cubic growth motif for small cluster sizes (n=6-9).
References[1] D.J. Harding, A. Fielicke, Chem. Eur. J. 20 (2014) 3258.
[2] Y.-C. Bae, V. Kumar, H. Osanai, Y. Kawazoe, Phys. Rev. B 72 (2005) 125427.
[3] Y.-C. Bae, H. Osanai, V. Kumar, Y. Kawazoe, Mater. Trans. 46 (2005) 159.
[4] D.J. Harding, T.R. Walsh, S.M. Hamilton, W.S. Hopkins, S.R. Mackenzie, P. Gruene,
M. Haertelt, G. Meijer, A. Fielicke, J. Chem. Phys. 132 (2010) 011101.
[5] D.J. Harding, C. Kerpal, D.M. Rayner, A. Fielicke, J. Chem. Phys. 136 (2012) 211103.

Tuesday September 9th

HT8Energetics, edge geometries, and electronic properties of silicene
Susumu Saito1-3 and Takashi Koretsune1,4
1
2

Department of Physics, Tokyo Institute of Technology, Tokyo, Japan

International Research Center for Nanoscience and Quantum Physics,
Tokyo Institute of Technology, Tokyo, Japan

3

Materials Research Center for Element Strategy, Tokyo Institute of Technology,Yokohama,Japan
4Center for Emergent Matter Science, RIKEN, Wako, Saitama, Japan

Ever since graphene was successfully produced in 2004, atomic-layer materials have been
attracting much attention due partly to their interesting electronic properties and partly to theirpotential importance as future device materials. In this regard, silicene, the Si atomic-layermaterial, is of great scientific and technological importance. Electronically silicene is expected topossess massless Dirac electrons as in the case of graphene while its geometry is different fromgraphene because the silicene plane is to be buckled. Theoretically, electronic properties offree-standing silicene have been studied well while experimentally silicene has been produced
only with substrates. In the framework of the density-functional theory we study silicene and its
composite atomic-layer materials in order to clarify their energetics and electronic properties. We
also study the edge geometries of not only the free-standing silicene but also the silicene on
substrates. It is found that silicene shows much larger reconstruction of edge atoms thangraphene, and buckling is strongly enhanced around the edge (Figure 1). Finally, we also discuss
the relative stabilities of three-dimensional Si clusters and silicene flakes to clarify the preferable
conditions to produce silicene.

Figure 1. Geometry of silicene nanoribbon

Tuesday September 9th

HT9One-dimensional uneven structured exotic-nanocarbon: Geometric curvature effects at nanoscale
Jun Onoe

Department of Physical Science and Engineering, Nagoya University, Nagoya, JapanIn 1916, A. Einstein first applied Riemannian geometry to physics for developing the general
theory of relativity and predicted the time-space strained by gravitational field. Four years later, his
prediction was demonstrated by the observation of a gravitational lens. This can be regarded asgeometric curvature effects on photonic properties.
It is of great interest to examine whether or not the geometric curvature effects affects theelectronic properties of condensed matters that are extremely smaller than the universe.
Although Riemannian geometry has been applied to quantum mechanics since 1950s forconsidering the electron behaviors on curved spaces, nobody could have hitherto answered thisquestion, because the electronic properties of materials with geometric curvature shapes havenever been examined experimentally.
We have fabricated a new form of nanocarbon from electron-beam (EB) irradiation of C60 films[1–11], and found the formation of a one-dimensional (1D) peanut-shaped C60 polymer exhibiting
the electronic, optical, and phonon properties of 1D metal [12–16]. Since the peanut-shaped C60
polymer has both positively and negatively Gaussian curvatures (k), it can be regarded as a new
nanocarbon allotrope (exotic-nanocarbon) that differs from graphene (k = 0), fullerenes (k > 0),nanotubes (k = 0 in body, k > 0 at cap edge), and the hypothetical Mackay crystal (k < 0). Thus,
the exotic-nanocarbon can be expected to exhibit novel properties different from those of thenanocarbon allotropes.
In this talk, we will demonstrate the geometric curvature effects on the electronic properties basedon Tomononaga-Luttinger Liquids [15], which has been predicted by our group [16], by examining
in situ high-resolution photoemission spectra of the 1D metallic uneven peanut-shaped C60
polymer film.
References[1] J. Onoe et al., Appl. Phys. Lett. 82, 595 (2003)[2] J. Onoe et al., Appl. Phys. Lett. 85, 2741 (2004)[3] T.A. Beu, J. Onoe, and A. Hida, Phys. Rev. B 72, 155416 (2005)[4] S. Ueda, Y. Noguchi, T. Ishii, J. Onoe, and K. Ohno, J. Phys. Chem. B 110, 22374 (2006)[5] T.A. Beu and J. Onoe, Phys. Rev. B 74, 195426 (2006)[6] J. Onoe et al., Phys. Rev. B 75, 233410 (2007)[7] Y. Toda, S. Ryuzaki, and J. Onoe, Appl. Phys. Lett. 92, 094102 (2008)[8] J. Onoe et al., J. Appl. Phys. 104, 103706 (2008)[9] A. Takashima, T. Nishii, and J. Onoe, J. Phys. D : Appl. Phys. 45, 485302 (2012)[10] S. Ryuzaki, M. Nishiyama, and J. Onoe, Diamond & Relat. Mater. 33, 12 (2013)[11] A. Takashima,J. Onoe, and T. Nishii, J. Appl. Phys. 108, 033514 (2010)[12] J. Onoe et al., Appl. Phys. Lett. 97, 241911 (2010)[13] J. Onoe et al., J. Phys.: Condens. Matter 24, 175405 (2012)[14] S. Ryuzaki and J. Onoe, Appl. Phys. Lett. 104, 113301 (2014)[15] J. Onoe et al., Europhys. Lett. 97, 27001 (2012)[16] H. Shima, H. Yoshioka, and J. Onoe, Phys. Rev. B 79, 201401 (R) (2009)

Tuesday September 9th

HT10

The Formation of Supported Carbon Clusters During Graphene Chemical Vapor
Deposition (CVD) GrowthFeng Ding, Qinghong Yuan, Junfeng Gao, Haibo Shu, Xiuyun Zhang, Ziwei Xu
Institute of Textile and Clothing, Hong Kong Polytechnic University, Hong Kong, PR China

The epitaxial CVD growth on catalyst surface is the most promising method of synthesizing highquality, large area graphene. A complete growth process includes (i) the nucleation of graphene
domains, (ii) the expansion the domain and (iii) the coalescence of the graphene domains into amacroscopic graphene layer. I’m going to present our recent theoretical studies on (i) in detail and(ii) in brief:
During the nucleation stage on most catalyst surface, C chains that have up to 8-13 C atoms arefound very stable and a transition from sp1 one dimensional (1D) C chain to sp2 two dimensional(2D) graphene island is necessary to initiate the graphene nucleation.[1-2] The metal step was
found to be the preferred site of graphene nucleation on catalyst surface and the medium sized C
cluster, C21, showed exceptional stability on the catalyst surface; [3-4]Edge construction is crucial for graphene in vacuum, while graphene edge on catalyst prefers tomaintain its pristine form. [5] While the naked graphene edge on Cu(111) surface tends to beterminated by Cu add atoms and the special passivation contribute to the fast growth rate ofgraphene armchair edge; [6]Three modes of graphene CVD growth, on terrace, near metal step, and the embedded growth areproposed and the graphene epitaxy growth or the determination of graphene’s orientation onvarious catalyst are carefully studied; [7-8]References:[1] J. F. Gao, et. al., J. Phys. Chem. C, 115 (36), 17695, (2011)[2] J. F. Gao, et. al., J. Am. Chem. Soc., 133(13), 5009, (2011)[3] Q. H. Yuan, et. al., J. Am. Chem. Soc., 133(40), 16072, (2011)[4] Q. H. Yuan, et. al., J. Am. Chem. Soc., 134, 2970-2975, (2012)[5] J. F. Gao, et. al., J. Am. Chem. Soc, 134, 6204-6209, (2012)[6] H. Shu, et. al., ACS Nano, 6, 3243-3250 (2012)[7] X. Y. Zhang, et. al., J. Phys. Chem. Lett., 3, 2822, (2012)[8] Q. H. Yuan, et. al., submitted

Tuesday September 9th

INV9

Effects of electronic and geometric structure on the activity of size-selectedmodel catalysts and electrocatalysts
Alexander von Weber, Eric Baxter, Matthew Kane, Sloan Roberts, and Scott Anderson
Department of Chemistry, University of Utah, Salt Lake City, UT, USA
Mass-selected cluster deposition is used to prepare model catalysts and electrodes for in situ
studies of both chemical and physical properties.

The goal, in addition to looking forcluster/support combinations with interesting catalytic activity, is to use size-dependent
correlations of activity with various physical or spectroscopy properties, to identify which propertiesof the samples are responsible for controlling activity.

Electronic structure is probed by a

combination of X-ray and UV photoelectron spectroscopies. Sample morphology, including thenature of reactant binding sites, is probed by low energy He+ scattering. Reactivity is probed
using either mass spectrometry, for gas-surface reactions, or by electrochemical measurements,
in the case of size-selected electrodes.
Results will be presented for CO oxidation and ethylene dehydrogenation over Pdn and Ptn
clusters on several different oxide supports, where strong support thickness- and size-dependent
correlations are seen between activity and both electronic structure and the availability of specificsites for oxygen activation. Results for the electrochemical ethanol oxidation, hydrogen evolution,and oxygen reduction reactions over Ptn on ITO and glassy carbon will also be discussed. Heretoo, there appear to be strong correlations between the electronic properties of the supported
clusters, and their activity as oxidation catalysts.

Tuesday September 9th

INV10

Plasmonic Property of Multidimensional Self-assembled Metallic Nanoparticles
Kaoru Tamada*Institute for Materials and Engineering (IMCE), Kyushu University, Fukuoka, Japan
In this paper, we report a fundamental optical property of self-assembled multidimensional metallic
nanoparticle sheets fabricated by Langmuir-Schaefer method at air-water interface. The 2D and
3D Ag self-assembled nanoparticle sheets exhibit a unique optical property due to the collective
excitation of localized surface plasmon resonance (LSPR). The homogeneously coupled LSPR in
2D sheet results in not only a significant red-shift and sharpened LSPR band but also an additional
amplification of electric field at the interface [1]. We also found that the multilayered Ag and Au
particle films on metal substrates exhibit a drastic reflection color change due to the number ofdeposited layers [2, 3], where a unique light confinement takes place together with 3D LSPR
coupling. We have also studied the characteristics of gold and silver (AuNP/AgNP) mixed
nanoparticle film fabricated by spreading AuNP/AgNP mixed solutions. The UV-vis absorption
spectra and the FDTD simulation revealed that the LSPR of AuNP and AgNP were not coupledeach other even when their resonance wavelength was overlapped by their domain size control.
Recently we also confirmed that the nanoparticle sheet provides highly confined and enhanced
fluorescence signals (LSPR field-enhanced fluorescence) [4]. The Ag nanoparticle sheet enabled
to provide 4 times enhanced fluorescence image with 160 nm spatial resolution in 30 msec/frame
shot under the total internal reflection fluorescence (TIRF) microscope. In the presentation,nano-patterning of the sheets by use of local oxidation nanolithography (LON) and their surface
potential change are also discussed.
References[1] M. Toma, K. Toma, K. Michioka, Y. Ikezoe, D. Obara, K. Okamoto, K. Tamada, Phys. Chem.
Chem. Phys. 12, (2012) 14749.
[2] K. Okamoto, B. Lin, K. Imazu, A. Yoshida, K. Toma, M. Toma, K. Tamada, Plasmonics, 8,(2013) 581,
[3] A. Yoshida, K. Imazu, X. Li, K. Okamoto, K. Tamada, Langmuir, 28, (2012) 17153.
[4] E. Usukura, S. Shinohara, K. Okamoto, J. Lim, K. Char, K. Tamada, Appl. Phys. Lett., 104,
(2014)121906.

Tuesday September 9th

HT11

Surface Plasmons in Quantum-Sized Noble-Metal Clusters: Quantum
Calculations and the Classical Picture of Charge Oscillations
Hans-Christian Weissker1,2 and Xóchitl López-Lozano3
1
2
3

CINaM-CNRS & Aix-Marseille Univ., 13288 Marseille, France.

European Theoretical Spectroscopy Facility, France; www.etsf.eu.

Department of Physics and Astronomy, The University of Texas at San Antonio. One UTSA
Circle, San Antonio, Texas 78249, USA

The localized surface-plasmon resonance (LSPR) in metal clusters corresponds to a collective
charge oscillation of the quasi-free electrons of the metal. In the present work, we use thereal-time

formulation

[1]

of

time-dependent

density-functional

theory(TDDFT)with

pseudopotentials to study the correspondence and differences of the quantum calculations withthe classical picture.
By means of animations, we discuss the real-time evolution of the electronic density for
different geometries. While there is a clear correspondence between the overall picture of acharge oscillation and the actual dynamics in quantum-sized clusters, the situation is much more
intricate owing to quantum effects and the inhomogeneity of the cluster due to the presence of thed electrons. A fine pattern is present over the volume of the cluster even at moments of zero
overall polarization. The difference between Ag and Au is clearly visible. Finally, we discuss thequestion of collective vs. molecular-like transitions, showing that even in the case of single
transitions, the dynamics of the total density can be similar to the picture of a charge oscillation.

Figure: Snapshot of the density dynamics showing the longitudinal charge
oscillation in a 37-atom Ag nanorod.

References[1] Yabana, K.; Bertsch, G. F., Phys. Rev. B 54, 4484 (1996).
[2] Weissker, H.-Ch., Whetten, R.L., and López-Lozano, X.; PCCP 16, 12495 (2014).
[3] López-Lozano, X.; Barron, H.; Mottet, C.; Weissker, H.-Ch., PCCP 16, 1820 (2014).

Tuesday September 9th

HT12

Clusters for Photocatalysis
Gunther Andersson,1 Gregory Metha,2 Vladimir Golovko,3 Tomonobu Nakayama,4 Koji Kimoto,4Hassan Al Qahtani,1, 4 Jason Alvino,2 Trystan Bennett,2 Jan-Yves Ruzicka,3 David P. Anderson,3Rantej Kler,1, 2 and Rohul Adnan 3
1

Flinders Centre for NanoScale Science and Technology, Flinders University, Adelaide, Australia
2

School of Chemistry and Physics, The University of Adelaide, Adelaide, Australia

3

Department of Chemistry, University of Canterbury, Christchurch, New Zealand
4

National Institute for Material Science, Tsukuba, Japan

Gold clusters with a size < 1.5 - 2 nm deposited and immobilized onto inert supports are known tobe catalytically active with the size threshold often coinciding with the loss of metallic properties of
Au nanoparticles. The size threshold has been established for both naked clusters prepared under
UHV conditions [1] and chemically-synthesised well-defined metal nanoparticles [2]. Clusters canbe deposited from the gas phase as size selected clusters [3] or from the liquid phase when usingchemically synthesised nanoparticles [4] with the latter route offering the benefit of easy scale-up.
A few challenges need to be solved regarding the deposition process of chemically made clusters
onto inert supports. First, it must be investigated whether removal of the ligands is required tomake the chemically made clusters catalytic active. The presence of ligands might hinder gas
molecules from accessing the catalytically active sites of the clusters. We have found that removalof phosphorous ligands can be achieved by heating to around 200ºC in vacuum [4]. Second, theagglomeration of the clusters must be avoided in order to keep the cluster size small. In particularheating for ligand removal could lead to agglomeration. We have deposited Aun(PPh3)y (n = 8, 9
and 101, y depending on the cluster size) on titania and found that treatment of the titania prior todeposition influences the agglomeration during ligand removal. Treatments applied include basic
and acidic treatment, calcination under H2 and O2 and UV/ozone treatment. Electron spectroscopy
techniques (X-ray photoelectron spectroscopy (XPS)), scanning techniques (atomic force
microscopy (AFM)) and microscopy ((scanning) transmission electron microscopy (STEM andTEM) have been used to investigate the deposition process. Subsequent to deposition, theelectronic and conformational structure must also be determined as these two properties are
believed to play a crucial role in catalysis. Metastable induced electron spectroscopy (MIES) has
been used to determine the electronic structure of deposited clusters.
References[1] M. Valden, X. Lai, and D. W. Goodman, Science 281(1998) 1647.
[2] M. Turner, V. B. Golovko, O. P. H. Vaughan, P. Abdulkin, A. Berenguer-Murcia, M. S. Tikhov, B.
F. G. Johnson, and R. M. Lambert, Nature 454(2008) 981.
[3] M. Büttner and P. Oelhafen, Surface Science 600, 1170 (2006).
[4] D. P. Anderson, J. F. Alvino, A. Gentleman, H. A. Qahtani, L. Thomsen, M. I. J. Polson, G. F.
Metha, V. B. Golovko, and G. G. Andersson, PCCP 15, 3917 (2013).

September 10th, Wednesday
9:00

Gold and silver in nanoscale, dispersed by ligands to molecular precision
Hannu Häkkinen (Invited)
9:40
Density functional theory investigations of gold and silver nanoparticle properties
Christine Aikens (Invited)
10:20 Electronic communication between metallic moiety and organic functionalities inultrasmall organic-modified gold clusters
Katsuaki Konishi
10:40 Coffee break
11:10 Motions of individual biomolecular motors probed by gold nanoparticle and nanorod
Ryota Iino (Invited)
11:50 Tracking photo-emitted electrons from gold nanoparticles by femtosecond laserdriven confocal microscopy
Marcel Di Vece
12:10 Functionalization of boron nitride nanosheets by a metal support for the oxygen
reduction reaction
Andrey Lyalin
12:30 Excursion
19:00 Conference dinnerWednesday September 10th

INV11Gold and silver in nanoscale, dispersed by ligands to molecular precision
Hannu Häkkinen1,2,3
1
23

Department of Chemistry,

Department of Physics, andNanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä, Finland

Nanometer-scale, ligand-stabilized noble metal clusters have emerged in recent years as a novel
form of nanoscale matter with potential applications in molecular electronics, optics, sensing, drugdelivery and biolabeling. Tremendous advances have been achieved in understanding theirstability and structure due to contributions from synthetic work, X-ray crystallography and density
functional theory computations. Their electronic structure can be understood surprisingly well fromthe simple concepts that have been used in the related field of bare gas-phase metal clusters
since 1980’s, particularly from the so-called “superatom model” that accounts for the delocalized
sp-electrons in the metal core.1,2 Forming in most cases the frontier orbitals of the nanoparticle,
these electrons are responsible for low-energy optical transitions and much of the chemistry.
Recent progress in understanding the structure as well as physical and chemical properties of thisclass of “superatoms” is reviewed,3-8 and a novel application of using atomically precise,functionalized thiol-stabilized gold nanoclusters for site-specific conjugation to enteroviruses for
TEM imaging is discussed.9
References[1] M. Walter et al., Proc. Natl. Acad. Sci (USA) 105, 9157 (2008).
[2] H. Häkkinen, Chem. Soc. Rev. 37, 1847 (2008).
[3] H. Häkkinen, Nature Chemistry 4, 443 (2012).
[4] H. Yang et al., Nature Communications 4, 2422 (2013).
[5] H. Yang et al., J. Am. Chem. Soc. 136, 7197 (2014).
[6] S. Malola et al., J. Phys. Chem. Lett. 2, 2316 (2011).
[7] S. Malola et al., ACS Nano 7, 10263 (2013).
[8] M. Azubel et al., submitted (2014).
[9] V. Marjomäki et al., Proc. Natl. Acad. Sci (USA) 111, 1277 (2014).

Wednesday September 10th

INV12Density Functional Theory Investigationsof Gold and Silver Nanoparticle Properties
Christine M. Aikens
Kansas State University, Manhattan, KS 66506, USA
Theoretical investigations of monolayer-protected noble metal nanoparticles play an important rolein determining the origins of the unique chemical and physical properties of these systems thatlead to applications in photonics, sensing, catalysis, etc. Density functional theory (DFT) andtime-dependent DFT (TDDFT) have been employed to calculate chemical reactivity and physicalproperties for a number of gold and silver nanoparticles of experimental interest.
Small thiolate-stabilized nanoparticles are of interest for their catalytic, fluorescent, and sensing
properties. TDDFT calculations have recently been employed to elucidate the excitation spectrumof Au25(SR)18 and related nanoparticles. This particle can be interpreted as a "superatom", inwhich a core of essentially free electrons is surrounded by gold-thiolate oligomeric ligands. The
ligand field arising from the surrounding gold-thiolate oligomers is responsible for the splitting of
the intraband transition. In addition, we will examine the “magic” Au38(SR)24 nanocluster. Using a
combination of electronic structure calculations, XRD, and optical and CD spectra, thisnanocluster is shown to be chiral with D3 symmetry. Au38(SR)24 is found to have an elongatedstructure; the electronic structure of this elongated “nanorod” is similar to that previously
determined for silver nanorods.

As for Au25(SR)18, delocalized superatom-like orbitals are

responsible for its properties.
Silver-DNA systems have been of interest for many years because these small systems arefluorescent and can be used as biotags. However, the structures of these systems are not yet
known. In this work, we show that slightly bent, twisted nanowires could explain the opticalabsorption and circular dichroism (CD) spectra of these interesting experimental systems.

Wednesday September 10th

HT13

Electronic communication between metallic moiety and organic functionalities
in ultrasmall organic-modified gold clusters
Katsuaki Konishi,1,2 Naoki Kobayashi,1 and Yukatsu Shichibu1,2
1

Graduate School of Environmental Science, Hokkaido University, Sapporo, Japan
2

Faculty of Environmental Earth Science, Hokkaido University, Sapporo, Japan

In the chemistry of ligand-protected metal clusters, the interaction between the metallic core andsurround organic moieties has been of unexplored but important subjects.

The interaction

between π-system and a gold core is especially interesting because it potentially offers uniquechemistry. During the course of study on diphosphine-ligated Au clusters [1-3], we have recently
found [core+exo]-type clusters [Au8(dppp)4X2]2+ having organic ligands (X) appended on theterminal exo gold atoms of the Au8 unit [1]. In this presentation we demonstrate a π-mediatedelectronic communication event between the gold unit and distal organic functionality in the
acid-induced chromism of pyridylethynyl-modified Au8 clusters [4].
Au8 clusters bearing two alkynyl ligands [Au8(dppp)4(C≡CR)2]2+ were synthesized by the reactionof the reduced form ([Au8(dppp)4]2+) with alkynyl anions. Although the C≡C moieties directly
attached to the Au8 units did not affect the optical properties arising from intracluster transitions [3],the pyridylethynyl-bearing clusters exhibited reversible visible absorption and photoluminescence
responses to protonation/deprotonation events of the terminal pyridyl moieties. The chromism
behaviors were highly dependent on the relative position of the pyridine nitrogen atom, suggestingthat the resonance-coupled movement of the positive charge upon protonation is involved in the
optical responses.

Thus the formation of extended charged resonance structures causes

significant perturbation effects on the electronic properties of the Au8 unit. These observations
provide an example of resonance-coupled transmission of chemical information to a distal cluster
unit through π-conjugated groups, and also demonstrate the utility of the combination with organic
chemistry in the design of cluster-based responsive systems.

References[1] Y. Kamei, Y. Shichibu, and K. Konishi, Angew. Chem. Int. Ed., 50, (2011) 7442.
[2] Y. Shichibu, Y. Kamei, and K. Konishi, Chem. Commun., 48, (2012) 7559.
[3] Y. Shichibu and K. Konishi,, Inorg. Chem., 52, (2013) 6570.
[4] N. Kobayashi, Y. Kamei, Y. Shichibu, and K. Konishi, J. Am. Chem. Soc.,135, (2013) 16078;
JACS spotlights, J. Am. Chem. Soc.,135, (2013) 17237.

Wednesday September 10th

INV13

Motions of individual biomolecular motors probed bygold nanoparticle and nanorod
Ryota Iino1,2
1

Okazaki Institute for Integrative Bioscience, Institute for Molecular Science,
National Institutes of Natural Sciences, Aichi, Japan2

Department of Functional Molecular Science, School of Physical Sciences,

The Graduate University for Advanced Studies (SOKENDAI), Kanagawa, Japan
Advances in optical microscopy have made it possible to watch individual biological molecularmachines in action. Just by watching and making the movies of single molecules, we can learn a
lot about their dynamic properties. The most successful examples of this approach are rotary andlinear molecular motors made of proteins [1, 2]. Molecular motors generate mechanical forces thatdrive their motions from the energy of chemical reaction. Molecular motors move fast, precisely,and efficiently. Our efforts have helped much to understand the operation mechanisms supporting
sophisticated behaviors of molecular motors.
We have recently developed new laser dark-field microscopes [3]. Our new microscopes candetermine the centroid position of single gold nanoparticle with microsecond temporal resolution
and one-nanometer localization precision, or the three dimensional orientation of single gold
nanorod with microsecond temporal resolution and one-degree angle precision. These methods
can be applied to the high-speed single-molecule imaging of the molecular motors by using gold
nanoparticle or nanorod as a probe. We can monitor not only the detail of motions such asmechanical steps generating force and pauses waiting for elementary steps of chemical reaction,
but also conformational changes inside individual molecular motors. In my presentation, I will
introduce our recent data on a rotary motor F1-ATPase and a linear motor kinesin (Fig. 1).

Fig. 1. (Left) a rotary motor F1-ATPase. (Right) a linear motor kinesin.
References[1] R. Iino, H. Noji, Curr. Opin. Struct. Biol. 23 (2013) 229-234.
[2] R. Iino, H. Noji, IUBMB Life. 65 (2013) 238-246.
[3] H. Ueno, S. Nishikawa, R. Iino, K.V. Tabata, S. Sakakihara, T. Yanagida, H. Noji, Biophys. J.
98 (2010) 2014-2023.

Wednesday September 10th

HT14

Tracking photo-emitted electrons from gold nanoparticles by femtosecond
laser-driven confocal microscopy
Wiebke Albrecht1, Wingjohn Tang1, Alfons van Blaaderen1, Marcel Di Vece1 2
1Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University
2

Nanophotonics, Debye Institute for Nanomaterials Science, Utrecht University

A wealth of fascinating phenomena are associated with the plasmonics of metal nanostructures.
Local field enhancement and phased array antennas are examples of how interaction of metalnanostructures with light provides interesting physics with in addition technological relevance.
Recent work showed that metallic nanostructures are able to emit photoelectrons, even whenbeing excited with laser energies well below the work function of the metal [1,2]. The
photoelectrons originating from the metal nanostructure are captured by the local (strong)
plasmonic field and moreover, are accelerated strongly by the same field. The acceleration
provides energies to the electron which are far above the laser excitation energy [3]. Eventually
the propelled electron is emitted and can be detected by electron spectrometry which is sensitive
to direction and energy. Not only would visualizing the electron trajectories be revealing, it would
also make the study of how such accelerated electrons interact with their environment for instanceby the detection of possible (intermediate) reactions much easier.
We present a study in which we imaged the electroluminescence trails of photoelectrons emitted
from gold clusters by femto second laser confocal microscopy. As far as we know the emitted
electron paths are visualized for the first time. The direction of the paths are governed by thescanning direction of the microscope but also by the laser polarization [4]. A complicated reaction
chain with trapped electrons which are reaccelerated provides insight into the dynamics of thisnovel and complicated system. We analyzed several cluster densities to obtain the optimal
condition for this process.
The gold clusters were prepared by a gas aggregation magnetron sputtering cluster source anddeposited on glass in the soft landing regime. This ensures a spherical shape and the vacuum
provides an ultra-clean surface. A state-of-the-art confocal microscope with an integrated
high-intense Ti:Sapphire fs-laser (Leica SP8) was used to image the electron trails.
Better control and understanding of this intriguing fundamental process can lead to the creation ofultrafast electron sources on the nanoscale.
Reference(s)[1] G. Herink, et al., Nature, 483 (2012) 190[2] A. Grubisic et al., Nano Lett. 12, (2012) 4823-4829[3] P. Dombi et al., Nano Lett. 13, (2013) 674-678[4] Th. Fennel et al., PRL 98, (2007) 143401

Wednesday September 10th

HT15

Functionalization of boron nitride nanosheets by a metal support for theoxygen reduction reaction
Andrey Lyalin,1 Akira Nakayama,1,2 Kohei Uosaki,3 and Tetsuya Taketsugu1,2
1

Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto, Japan2
3

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Global Research Center for Environment and Energy based on Nanomaterials Science(GREEN), National Institute for Materials Science (NIMS), Tsukuba, Japan

It is demonstrated that boron nitride (BN), which is catalytically inert insulator with a wide band gap,
can be functionalized and act as an electrocatalyst for oxygen reduction reaction (ORR). Suchfunctionalization can be achieved by the nitrogen doping [1] or deposition of the BN nanosheets onsome transition metals, such as Ni(111) [2] or Au(111) [3]. Density-functional theory calculations
show that interaction of BN nanosheets with the metal supports results in formation of the bandstates in the forbidden zone of BN, as it occurs in the case of Ni(111) support [2] or a slight
protrusion of the unoccupied BN states toward the Fermi level as it observed for Au(111) support[3]. Modification of the BN band structure can be explained by the orbital mixing and electron
sharing at the interface [4,5]. Analysis of the binding preference and adsorption energies of the
ORR intermediates on functionalized BN nanosheets demonstrate possibility of ORR. It is
experimentally proved that overpotential for ORR at the gold electrode is significantly reduced bydepositing BN nanosheets (Fig. 1). The present study demonstrates the possibility to functionalize
inert materials to become ORR catalysts, opening new ways to design effective Pt-free catalysts
for fuel cells based on materials never before considered as catalysts.
a)

b)

c)

Figure 1. Optimized structures of O2 adsorbed at the edge of the small h-BN island on the Au(111)
surface (a) and (b). The linear sweep voltammograms of (i) bare Au, (ii) BNNS/Au, (iii) bare glassy
carbon (GC), and (iv) BNNS/GC as well as free energy diagram for ORR on the h-BN/Au(111) (c).
References[1] A. Lyalin, A. Nakayama, K. Uosaki, and T. Taketsugu, PCCP 15 (2013) 2809.
[2] A. Lyalin, A. Nakayama, K. Uosaki, and T. Taketsugu, J. Phys. Chem. C 117 (2013) 21359.
[3] K. Uosaki, G. Elumalai, H. Noguchi, T. Masuda, A. Lyalin, A. Nakayama, and T. Taketsugu,
JACS 136 (2014) 6542.
[4] R. Laskowski, P. Blaha, K. Schwarz, Phys. Rev. B 78 (2008) 045409.
[5] A. B. Preobrajenski, S. A. Krasnikov, A. S. Vinogradov, M. L. Ng, T. Kaambre, A. A. Cafolla,
and N. Martensson, Phys. Rev. B 77 (2008) 085421.

September 11th, Thursday
9:00

Metal-polymer nanocomposites produced by supersonic cluster beam implantation
with tunable electrical, optical and mechanical properties
Paolo Milani (Invited)
9:40
Switching, tunneling, and superconductivity in percolating cluster films
Simon Brown (Invited)
10:20 Nanoisland formation of small AgN-clusters on HOPG as determined by inner-shell
photoionization spectroscopy
Matthias Neeb

10:40 Coffee break
11:10 Photophysical properties of supramolecular nanostructures in gas-phase
Manfred Kappes (Invited)
11:50 Channeling vibrational energy to probe the electronic density of states in metalclusters
Andrei Kirilyuk
12:10 Frontier orbital rule for electron transport in molecules
Kazunari Yoshizawa
12:30 Lunch
14:00 The 3D-architecture of individual free silver nanoparticles captured by X-ray
scattering
Karl-Heinz Meiwes-Broer (Invited)
14:40 Hidden charge states in soft-X-ray laser-produced nanoplasmas revealed byfluorescence spectroscopy
Tim Laarmann
15:00 The role of metal doping on the reversible adsorption and storage of hydrogen in
nanoporous carbons
Maria J. López
15:20 Photoelectron spectroscopy and density functional theory investigation of VxSi12−(x = 1-3) clusters: discovery of a silicon-based ferrimagnetic wheel structure
Xiaoming Huang
15:40 Co･Ar+ complexes: the smallest and most exotic bar magnets with giant magnetic
anisotropy energy
Tobias Lau
16:00 Coffee break
16:30 Poster Session B
18:30 Cultural event

Thursday September 11th

INV14

Metal-polymer nanocomposites produced by supersonic cluster beam
implantation with tunable electrical, optical and mechanical properties
A. Bellacicca1, F. Borghi1, A. Podestà1, C. Melis2,
L. Colombo2, C. Ghisleri3, L. Ravagnan3, P. Milani1
1

CIMAINA, Department of Physics, University of Milano, Milano, Italy2

Department of Physics, University of Cagliari, Cagliari, Italy
3

WISE srl, Milano, Italy

Stretchable functional materials are enabling ingredients for the fabrication of wearable
electronics, smart prosthetics and soft robotics. These applications require the integration ofelectronic, optical and actuation capabilities on soft, conformable and biocompatible polymeric
substrates [1].
Recently we demonstrated that neutral metallic nanoparticles produced in the gas phase andaerodynamically accelerated in a supersonic expansion can be implanted in a polymeric substrate
to form a conductive nanocomposite with superior resilience and interesting structural andfunctional properties [2-4]. This approach is called supersonic cluster beam implantation (SCBI).
Here we present experimental and theoretical results about the production of devices based on
metal/polymer nanocomposites with electrical, optical and mechanical properties that can be
precisely tuned by controlling the fraction of metal clusters implanted in the polymeric matrix [5-6].
State of the art applications and devices for stretchable optics, neurostimulation and soft robotics
will be shown and discussed.
References[1] S. Bauer, et al., Adv. Mater. 26, 149 (2014)[2] G. Corbelli, et al., Adv. Mater. 23, 4504 (2011)[3] C. Ghisleri, et al., Laser & Photonics Rev. 7, 1020 (2013)[4] C. Ghisleri, et al., Appl. Phys. Lett. 104, 061910 (2014)[5] R. Cardia, et al., J. Appl. Phys. 113, 224307 (2013)[6] C. Ghisleri, et al., J. Phys. D: Appl. Phys. 47, 015301 (2014)

Thursday September 11th

INV15

Switching, Tunneling, and Superconductivity in Percolating Cluster Films
S. A. Brown1, A. Nande1, S. Fostner1, R. Gazoni1, A. Smith1, A. Sattar1, J. Grigg1,
S. Couet2, K. Temst2, M.J. Van Bael3,
1

The MacDiarmid Institute for Advanced Materials and Nanotechnology, Dept. of Physics andAstronomy, University of Canterbury, 8140, Christchurch, New Zealand2

Instituut voor Kern- en Stralingsfysica, Celestijnenlaan 200 D, KU Leuven, Leuven B-3001,
Belgium

3

Laboratory of Solid State Physics and Magnetism, Celestijnenlaan 200 D, KU Leuven, Leuven
B-3001, Belgium

When clusters are randomly deposited on a surface they produce percolating films which haveremarkable electrical properties.[1] Here we will focus on devices that contain percolating films of
Sn and Pb clusters between a pair of electrical contacts, and especially those that are deliberately
constructed so as to guarantee that the film is close to the percolation threshold (onset of
conduction). In these devices quantum mechanical tunnelling is important[2], and several new andunexpected phenomena are observed. In particular we have recently demonstrated switching
between well-defined, quantized, conductance values [multiples of the quantum of conductance(2e2/h)], at room temperature.[3]Recently we have begun exploring the superconducting properties of these films. We find that thepercolating films have interesting characteristics that are intermediate between those of 1D and2D systems. We will discuss phase slips[4,5], which appear to occur in the narrow necks between
clusters, and the competition between percolation effects and the vortex unbinding associatedwith the Berenzinski-Kosterlitz-Thouless transition[6,7]. We will also discuss a superconductor toinsulator transition which can be driven by the applied current.
Reference(s)[1] J. Schmelzer jr, S. A. Brown, A. Wurl, M. Hyslop, and R. J. Blaikie, Phys. Rev. Lett. 88,
226802 (2002).
[2] S. Fostner, R. Brown, J. Carr, and S. A. Brown, Phys. Rev. B 89, 075402 (2014).
[3] A. Sattar, S. Fostner, and S. A. Brown, Phys. Rev. Lett. 111, 136808 (2013).
[4] A. Nande et al, to be published.
[5] J. S. Langer and Vinay Ambegaokar, Physical Review 164, 498 (1967); W. A. Little, PhysicalReview 156, 396 (1967).
[6] V. L. Berezinskii, Sov. Phys. JETP 34, 610 (1972); J. M. Kosterlitz and D. J. Thouless, J. Phys.
C 6, 1181 (1973).
[7] S. Fostner et al, to be published.

Thursday September 11th

HT16

Nanoisland formation of small AgN-clusters on HOPG as determined byinner-shell photoionization spectroscopy
M. Neeb1, M. Al-Hada2, S. Peredkov3, S. Peters3, W. Eberhardt3,412Helmholtz-Zentrum Berlin, BESSY II, Berlin, Germany

Department of Physics, Amran University, Amran, Jemen
3

4

IOAP, Technical-University Berlin, Berlin, Germany

Center for Free Electron Laser Science cFEL, DESY, Hamburg, Germany

Small Ag-clusters represent highly interesting particles for optoelectronic applications due to theirquantum-sized electronic properties like tunable plasmon frequencies, fluorescence activity andmetal-biomolecule hybrid formation [1,2,3]. Moreover Ag-particles dispersed on planar supports
such as oxides and carbon represent an important type of heterogeneous catalysts [4,5] as well as
nanocomposite material for tunable electronic and optical applications of e.g. graphene [6,7].
In

general,element-specific

X-ray photoionization

studies have been demonstrated to be useful for theinvestigation of deposited clusters [8]. Here we show by
the application of XPS and Auger spectroscopy that
small Ag-clusters coalesce into bulk-like nanoislands
upon deposition onto the surface of pristine HOPG, afew-layer model of graphene. In case of oxidation of themetallic islands a positive binding energy shift (XPS) is
observed in distinct contrast to the negative chemical
shift usually observed for oxidized silver compounds.
This is interpreted by an electrostatic Coulomb shift of the oxidized Ag-islands from which the sizeof the nanoislands has been determined according to the electric potential of a charged disc.
References[1] L.A. Peyser, A.E. Vinson, A.P. Bartko, R.M. Dickson, Science 291, 103 (2001).
[2] C. Félix, C. Sieber, W. Harbich, J. Buttet, I. Rabin, W. Schulze, G. Ertl, PRL 86, 2992 (2001).
[3] T. Tabarin, A. Kulesza,R. Antoine, R. Mitric, M. Broyer, P. Dugourd, V. Bonacic-Koutecky,
PRL 101, 213001 (2008).
[4] D.V. Demidov. I.P. Prosvirin, A.M. Sorokin, V.I. Bukhtiyarov, Catal. Sci. Technol., 1, 1432 (2011).
[5] V. I. Bukhtiyarov, M. Hävecker, V. V. Kaichev, A. Knop-Gericke, R. W. Mayer, R. Schlögl, Phys. Rev.
B 67, 235422 (2003).
[6] Z. Li, P. Zhang, K. Wang, Z. Xu, J. Wei, L. Fan, D. Wu, H. Zhu, J. Mater. Chem. 21, 13241, (2011).
[7] G. Lu, S. Mao, S. Park, R.S. Ruoff, J. Chen, Nano Res. 2, 192 (2009).
[8] S. Peters, S. Peredkov, M. Al-Hada, M. Neeb, W: Eberhardt, Surf. Sci. 608, 129 (2013) andreferences therein.

Thursday September 11th

INV16

Photophysical properties of supramolecular nanostructures in gas-phase

Manfred Kappes,1,2 Patrick Weis,1 Detlef Schooss, 2 Oliver Hampe, 2† Jean-Francois Greisch, 2Matthias Vonderach, 1 Ulrike Schwarz,1 Patrick Jäger 2 and Marc-Oliver Winghart 1
1

Institute of Physical Chemistry, KIT, Karlsruhe, Germany
2

Institute of Nanotechnology, KIT, Karlsruhe, Germany†

deceased 23.4.14

Electrospray ionization (ESI) can be used to isolate fragile, self-assembled supramolecularorganometallic structures from solution.

Additionally, clusters and further adducts of suchspecies can be formed during the ESI process itself. Information on gas-phase structures andproperties can be obtained using methods well known from research on elemental clusters: highresolution mass spectrometry, ion mobility (IMS), anion photoelectron spectroscopy (PES),
photodissociation spectroscopy (PD) and trapped ion photoluminescence – sometimes incombination, e.g. IMS-PES [1] or IMS-PD. In this talk I will discuss applications to charged
aggregates of strongly absorbing metalloporphyrins [2] (and azoporphyrins [3]) as well-as tophotoluminescent lanthanide cluster complexes with organic antenna molecules [4].
References[1] M. Vonderach, O. T. Ehrler, P. Weis and M. Kappes, Anal. Chem. 83 (2011), 1108; M.
Vonderach, O. T. Ehrler, K. Matheis, P. Weis and M. Kappes, J. Am. Chem. Soc. 134 (2012)7830.
[2] T. Karpuschkin, M. Kappes and O. Hampe, Angewandte Chemie Int. Ed. 52 (2013),
10374-10377; U. Schwarz, M. Vonderach, M. Kappes, R. Kelting, K. Brendle and P. Weis, Int. J.
Mass Spec. 339 (2013), 24; U. Schwarz, M. Vonderach, M. Armbruster, K. Fink and M. Kappes,
J. Phys. Chem A 118 (2014), 369.
[3] P. Weis, U. Schwarz, F. Hennrich, D. Wagner, S. Bräse and M. Kappes, Phys. Chem. Chem.
Phys. 16 (2014), 6225.
[4] J.-F. Greisch, M. Harding, B. Schäfer, M. Rotter, M. Ruben, W. Klopper, M. Kappes and D.
Schooss, J. Phys. Chem. A 118 (2014), 94; J.-F. Greisch, M. Harding, B. Schäfer, M. Ruben,
W. Klopper, M. Kappes and D. Schooss, J. Phys. Chem. Lett., 5 (2014), 1727.

Thursday September 11th

HT17

Channeling Vibrational Energy to Probe the Electronic Density of Statesin Metal Clusters
Jeroen Jalink1, Joost M. Bakker2, Theo Rasing1, and Andrei Kirilyuk1
1

Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg 135,
6525 AJ Nijmegen, The Netherlands
2

Radboud University Nijmegen, Institute for Molecules and Materials, FELIX Facility,
Toernooiveld 7, 6525 ED Nijmegen, The Netherlands

Atomic clusters are the smallest pieces of matter where condensed matter properties gradually
emerge with the number of constituent atoms [1]. The physical and chemical properties of eachcluster vary strongly on an atom-by-atom level leading to intriguing magnetic [2], electric [3] andcatalytic [4] properties. An important factor in these phenomena is the electronic structure of theparticular cluster, which is thus of primary importance. The electronic structure of neutral clusters
can be probed using photoelectron spectroscopy (PES) of mass selected anionic clusters [5].
However, such PES studies are usually limited to the geometry of the anion. Since the geometricstructures of clusters can vary for different charge states, it is important to probe the electronic
structure of the neutral species directly. Direct spectroscopic studies on neutral transition metalclusters such as laser-induced fluorescence and resonance-enhanced multiphoton ionization have
only been reported for systems containing up to 3 atoms. It is likely that the large density ofelectronic states leads to a rapid electronic relaxation, precluding detection.
Here we demonstrate a method based on two-color IR-UV spectroscopy to probe the electronic
density of states near the Fermi level in neutral metal clusters. Our method consists of measuring
the UV ionization yield of clusters at different internal temperatures. The temperature is modulated
by resonantly pumping cluster lattice vibrations. Such excitation is followed by two processes: (1)intramolecular vibrational redistribution of the energy within ps and (2) energy flow from the lattice
into the electronic system. The time scale for the second process is determined by theelectron-phonon (vibronic) coupling and for transition metals it is of the order of ps. Our approachthus ensures a thermal equilibrium within the experimental time scale (~μs). Fowler’s model ofsurface photoemission is modified to incorporate the discrete nature of the electronic structure,
which allows to validate electronic structure calculations. Intriguingly, the energy redistribution
between vibrations and electrons could in principle be probed in a time-resolved experiment.
Reference(s)[1] W.A. de Heer, Rev. Mod. Phys. 65 (1993) 611.
[2] X. Xu, S. Yin, R. Moro, A. Liang, J. Bowlan, W.A. de Heer, Phys. Rev. Lett. 107 (2011) 057203.
[3] R. Moro, X. Xu, S. Yin, W.A. de Heer, Science 300 (2003) 1265.
[4] S.M. Lang, T.M. Bernhardt, R.N. Barnett, U. Landman, Angew. Chem. Int. Ed. 2010, 49, 980.
[5] C. Bartels, C. Hock, J. Huwer, R. Kuhnen, J. Schwöbel, B. von Issendorff, Science 323 (2009)1323.

Thursday September 11th

HT18

Frontier Orbital Rule for Electron Transport in Molecules
Kazunari Yoshizawa
Institute for Materials Chemistry and Engineering, Kyushu University
Nishi-ku, Fukuoka 819-0395, JAPANOur orbital view studies about molecular conductance for 10 years is presented. We havedeveloped a chemical way of thinking about electron transport in molecules in terms of frontier
orbital theory [1-4]. The phase and amplitude of the HOMO and LUMO of π-conjugated molecules
determine the essential properties of their electron transport. By considering a close relationshipbetween Green’s function and the molecular orbitals, we derived an orbital rule that would help our
chemical understanding of the phenomenon. First, the sign of the product of the orbital coefficients
at sites r and s in the HOMO should be
different from the sign of the product of
the orbital coefficients at sites r and s in
the LUMO for good electron transport, as
indicated in the scheme. Secondly, sitesr and s in which the amplitude of the
HOMO and LUMO is large should beconnected.

We

confirmed

these

theoretical predictions experimentally byusing break junctions to measure thesingle-molecule conductance of naphthalene dithiol derivatives [5]. The measurement of thesymmetry-allowed 1,4-naphthalene dithiol shows a conductance that exceeds that of thesymmetry-forbidden 2,7-naphthalene dithiol by two orders of magnitude.
The intermolecular electronic coupling in π-stacked structures plays an important role in theelectron conduction in extended systems. We studied a π-stacked benzene molecule[2,2]paracyclophane to investigate the effect of the intermolecular interactions in aromatichydrocarbons on its electron-transport properties [6]. The qualitative but essential understanding
in the orbital views would extend the application of the rule from a single molecule to a crystal
structure for the development of high performance molecular devices.
References[1] Yoshizawa, K. Acc. Chem. Res. 2012, 45, 1612.
[2] Tada, T.; Yoshizawa, K. ChemPhysChem 2002, 3, 1035.
[3] Yoshizawa, K.; Tada, T.; Staykov, A. J. Am. Chem. Soc. 2008, 130, 9406.
[4] Tsuji, Y.; Staykov, A.; Yoshizawa, K. J. Am. Chem. Soc. 2011, 133, 5955.
[5] Taniguchi, M.; Tsutsui, M.; Mogi, R.; Sugawara, T.; Tsuji, Y.; Yoshizawa, K.; Kawai, T. J. Am.
Chem. Soc. 2011, 133, 11426.
[6] Li, X.; Staykov, A.; Yoshizawa, K. Bull. Chem. Soc. Jpn. 2012, 85, 181.

Thursday September 11th

INV17

The 3D-architecture of individual free silver nanoparticles
captured by X-ray scattering
I. Barke1, D. Rupp2, H. Hartmann1, L. Flückiger2, M. Saupe3, M. Adolph2, Ch. Peltz1, S. Bartling1,
T. Fennel1, T. Moeller2, K.-H. Meiwes-Broer1
1

Institut of Physics, University of Rostock, Universitätsplatz 3, 18051 Rostock, Germany
2
Technical University of Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany
3
SLAC National Acceleretor Laboratory 2575 Sand Hill Road, Menlo Park, CA 94025

Identifying the morphology of free metal particles is one of the fundamental objectives in cluster
science. In recent years the most favorable shapes of metal clusters consisting of a small numberof atoms have been successfully solved based on a combination of theoretical and experimental
methods. However, for large unsupported clusters the structure determination remained difficult.
In this contribution we present single particle scattering images from free silver clusters obtainedat the free-electron laser facility FLASH using XUV photons with ≈ 13.5 nm wavelength. Singleshot x-ray scattering enables 3D characterization of the particles, which can be considered fixedin space for the duration of photon exposure. In contrast to previous results from rare gas clusters[1], anisotropic features with high symmetry
are observed, reflecting the regular shape ofmetal particles with radii larger than ≈ 40 nm.
A fast and versatile algorithm for simulation of
scattering images from arbitrarily shaped
three-dimensional particles is used that isbenchmarked against state-of-the-art finite
difference time domain simulations for selected morphologies and sizes. A variety of cluster morphologies can be identified, including
truncated octahedrons, decahedrons, twinned
tetrahedrons, and icosahedrons. Excellent
agreement is obtained between measured andsimulated scattering images demonstrating
the feasibility of reliable shape determinationof particles in the free beam. Moreover, therole of photon absorption could be revealed.
Scattering image from a 85 nm silver cluster of icosahedral shape, simulated with Finite Difference Time Domain (FDTD) calculations. Photon wavelength 13.5 nm
The observations show that energetically non-ideal morphologies continue to exist in the freebeam even for sizes exceeding 200 nm in diameter. Considering that icosahedral Ag particles arereported to undergo a transition to fcc structure with increasing cluster size [2], our results shed
new light on the growth of large particles in the gas phase.
References[1] C. Bostedt, E. Eremina, D. Rupp, M. Adolph, H. Thomas, M. Hoener, A. R. B. de Castro, J.
Tiggesbäumker, K.-H. Meiwes-Broer, T. Laarmann, H. Wabnitz, E. Plönjes, R. Treusch, J. R.
Schneider, and T. Möller, Phys. Rev. Lett. 108, 093401 (2012)[2] Baletto et al., J. Chem. Phys. 116 (2002)

Thursday September 11th

HT19

Hidden Charge States in Soft-X-Ray Laser-Produced Nanoplasmas
Revealed by Fluorescence Spectroscopy
L. Schroedter,1 M. Müller,2 A. Kickermann,1 A. Przystawik,1 S. Toleikis,1 M. Adolph,2 L. Flückiger,2T. Gorkhover,2 L. Nösel,2 M. Krikunova,2 T. Oelze,2 Y. Ovcharenko,2 D. Rupp,2 M. Sauppe,2 D.
Wolter,2 S. Schorb,3 C. Bostedt,3 T. Möller,2 and T. Laarmann1,4
12

Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany

Institut für Optik und Atomare Physik, Technische Universität Berlin, Berlin, Germany
3
4

SLAC National Accelerator Laboratory, Stanford, USA

The Hamburg Centre for Ultrafast Imaging CUI, Hamburg, Germany

A fascinating application of X-Ray Free-Electron Lasers (XFEL) is coherent diffraction imaging of
single particles in a single light pulse. However, a severe challenge is the damage done to the
biopolymers by the light pulse. Besides elastic scattering by bound electrons, strong ionization
takes place and the molecule is destroyed. It is an open question whether sufficient scattering
signal can be detected before the molecule disintegrates. One possible way to alleviate thisproblem is adding a sacrificial tamper layer around the molecule which slows down the expansion.
In the present contribution we discuss experiments on clusters as nanoscopic model systems totest the effect of tamper layers [1], as so-called core-shell clusters were generated, with a core
consisting of one element surrounded by a shell consisting of another element. By detecting
emitted fluorescence photons in the extreme ultraviolet spectral range we were able to derive
information on the first few hundred femtoseconds of the FEL interaction with the composite
clusters. The data recorded at the FLASH facility at DESY provide fingerprints of transient statesof high energy density matter. The experiments give direct evidence that - in addition to themultiply charged cluster surface which Coulomb explodes and finally leads to fluorescence fromindividual ions - also the cluster ion core is initially highly charged. During the FEL interaction andbefore disintegration, highly charged ions that have lost more than 10 electrons each are
generated and could clearly be identified by their characteristic radiative transitions. Therefore,
fluorescence spectroscopy probes ultrafast radiative decay of highly charged ions in a time
window which is not accessible by conventional mass spectrometry. In agreement with theory, thelatter traces remnants of the interaction, where electron thermalization followed by nonradiative
recombination has already produced significantly lower charge states. Thus, a sacrificial tamper
layer provides an efficient electron source for partial neutralization of highly charged ions createdin the center. The significant reduction of charge states increases the available time for recording
a diffraction pattern in coherent imaging experiments elucidating the three-dimensional structureof biopolymers.
Reference[1] L. Schroedter et al., Phy. Rev. Lett. 112 (2014) 183401.

Thursday September 11th

HT20

The role of metal doping on the reversible adsorption and storage of hydrogenin nanoporous carbons
María J. López, Iván Cabria, and Julio A. Alonso
Departamento de Física Teórica, Atómica y Óptica, Universidad de Valladolid, Valladolid, Spainmaria.lopez@fta.uva.es

Storage is the main problem to use hydrogen as an alternative fuel to gasoline in cars.
Nanoporous carbons, whose walls have an atomic structure formed of graphene-like ribbons withmany defects, are among the best candidate materials as containers. However, under the mild
conditions of technological interest (room temperature and moderate pressures) they exhibit alimited/poor storage capacity due to the weak adsorption of molecular hydrogen to the pore walls[1], below 0.1 eV per molecule. Experimental evidences suggest that doping the porous carbons
with metals may enhance their storage capacity although the mechanism is not well understood.
We have performed density functional calculations to investigate the reversible adsorption ofhydrogen on palladium doped nanoporous carbons, paying special attention to the problems thatarise in the desorption step. Our simulations on Pd atoms and clusters supported on graphenereveal that hydrogen binds directly to the Pd atoms and clusters following two different adsorption
modes: molecular adsorption and dissociative atomic chemisorption [2]. The energies formolecular adsorption are in the range appropriate for achieving reversible adsorption/desorption
at room temperature. However, desorption of the stored molecular hydrogen competes with otheralternative processes: a) dissociative chemisorption of hydrogen, after passing through theactivation barrier and b) desorption of Pd-H complexes. We have found that desorption of Pd-H
complexes can be successfully avoided by anchoring the Pd atoms and clusters to defects present
on the carbonaceous substrate [3]. In addition, we find that the presence of defects improves thedispersion of the metal on the carbon network with the consequent beneficial effect on the storage
capacity of the material.
Reference(s)[1] J.A. Alonso, I. Cabria, M.J. López , J. Mater. Res. Vol. 28 (2013) 589.
[2] I. Cabria, M.J. López, S. Fraile, J.A. Alonso, J Phys. Chem. C 116 (2012) 21179.
[3] M.J. López, I. Cabria, J.A. Alonso, J. Phys. Chem. C 118 (2014) 5081.
Acknowledgement: This work was supported by MICINN of Spain (Grant MAT2011-22781)

Thursday September 11th

HT21

Photoelectron Spectroscopy and Density Functional Theory Investigation of
VxSi12– (x = 1-3) clusters: Discovery of a Silicon-based Ferrimagnetic Wheel
Structure

Jijun Zhao,1 Xiaoming Huang,1 Xiaoqing Liang,1 Hong-Guang Xu,2 Shengjie Lu,2 Weijun Zheng 2
1

Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Dalian University ofTechnology, Dalian 116024, China
2

Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

We combine anion photoelectron spectroscopy and density functional theory (DFT) to examine thestructures as well as the electronic and magnetic properties of VxSi12– (x=1, 2, 3) clusters. Ourstudies show that VSi12– adopts a V-centered hexagonal prism with a singlet spin state. Addition of
the second V atom leads to a capped hexagonal antiprism for V2Si12– in a doublet spin state. Most
interestingly, V3Si12– exhibits a ferrimagnetic bicapped hexagonal antiprism wheel-like structurewith a total spin of 4 B and a HOMO-LUMO gap of 0.35 eV. The number of unpaired electrons inneutral and anionic V3Si12 cluster can be understood by the Wade-Mingos rules for polyhedralclusters.
In addition, our combined study of photoelectron spectroscopy and DFT calculations show that
Fe2Gen– and Cr2Gen– (n=3-12) clusters exhibit robust ferromagnetic and antiferromagnetic
behaviors, respectively, which are nearly irrelevant to the cluster size and geometry. All thesefindings not only extend our understanding of doped silicon/germanium clusters but also provide
novel building blocks for nanoscale spintronic devices.

Thursday September 11th

HT22

Co∙Ar+ complexes: The smallest and most exotic bar magnets withgiant magnetic anisotropy energy
Vicente Zamudio-Bayer,1,2 Konstantin Hirsch,1 Arkadiusz Ławicki,1 Akira Terasaki,3 Bernd vonIssendorff,2 and Tobias Lau1
1

Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung,Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin, Germany
2

Physikalisches Institut, Universität Freiburg, Freiburg, Germany

3

Department of Chemistry, Kyushu University, Fukuoka, Japan

In macroscopic magnets, the magnetization direction is rigidly fixed with respect to the geometricalshape by the magnetic anisotropy energy. This is why a macroscopic bar magnet, like a compass
needle, is aligned with an external magnetic field. The situation is usually different in smalltransition metal clusters, where the orientation of the magnetic moment can rotate freely against
the cluster body, and superparamagnetic behavior is typically found [1-3].
We have for the first time observed evidence of the geometrical alignment of small Co∙Ar+
complexes with an external magnetic field, thus creating the smallest and most exotic bar magnets,
consisting of only one magnetic ion bound to a rare gas atom. In these systems, the spin magnetic
moment is coupled to the intramolecular axis by more than 5 meV of magnetic anisotropy energy.
The magnetic and spatial alignment was probed by the simultaneous detection of X-ray naturallinear dichroism and X-ray magnetic circular dichroism of size-selected free Co∙Ar+ complexes at T
< 10 K and B = 5 T in a linear radio-frequency ion trap [3,4]. This technique will allow us to explore
the physical limits of the magnetic anisotropy energy in small transition metal clusters, molecules,
and complexes [5].
References[1] C. P. Bean and J. D. Livingston, J. Appl. Phys. 30 (1959) S120.
[2] P. Ballone, P. Milani, and W. A. de Heer, Phys. Rev. B 44 (1991) 10350.
[3] M. Niemeyer, K. Hirsch, V. Zamudio-Bayer, A. Langenberg, M. Vogel, M. Kossick, C. Ebrecht,
K. Egashira, A. Terasaki, T. Möller, B. v. Issendorff, and J. T. Lau, Phys. Rev. Lett. 108 (2012)057201.
[4] K. Hirsch, J. T. Lau, P Klar, A. Langenberg, J. Probst, J. Rittmann, M. Vogel, V. Zamudio-Bayer,
T. Möller, and B. von Issendorff, B. J. Phys. B: At. Mol. Opt. Phys. 42 (2009) 154029.
[5] T. O. Strandberg, C. M. Canali, and A. H. MacDonald, Nat. Mater. 6 (2007) 648.

September 12th, Friday
9:00

Tuning cluster functionality by size and compositionPeter Lievens (Invited)
9:40
Clusters as model systems for catalysis
Thorsten Bernhardt (Invited)
10:20 Stable stoichiometry and chemical reactivity of cluster ions revealed byhigh temperature TPD experiments
Fumitaka Mafuné
10:40 Coffee break

11:10 Extending the sizes and charge states of polyanionic metal clusters
Steffi Bandelow
11:30 Characterization of single-molecule magnets in isolation
Gereon Niedner-Schatteburg
11:50 Spin orientation in isolated magnetic nanoalloys - topology, dielectric andmagnetic properties of manganese doped tin-clusters Mn/SnN
Urban Rohrmann
12:10 ISSPIC 18
12:20 Concluding remarks and perspectives
Vlasta Bonačić-Koutecký (Invited)
13:00 Closing
Akira Terasaki

Friday September 12TH

INV18

Tuning cluster functionality by size and compositionPeter Lievens and Ewald Janssens
Department of Physics & Astronomy, Faculty of Science, KU Leuven, Belgium
Tuning cluster properties by their size and composition has been a long standing challenge incluster science, and has over the years been realized by the synthesis and study of a wide varietyof bimetallic, binary, and also some ternary clusters. One specific asset of studying mixed clusters
is the possibility to tailor independently the cluster geometry via the number of atoms and thecluster electronic properties determined by the number of (delocalized) electrons. From afundamental point of view this interplay of geometry and electronic structure is ideal to challenge
advanced quantum mechanical modeling as well as phenomenological descriptions of size andcomposition dependent properties. With respect to the role of nanoparticles and clusters innanotechnology applications, the atom by atom control of physical and chemical properties is an
important asset.
This talk will deal with growth, stability patterns, structure, electronic and optical properties andmagnetism of small binary metal clusters, in particular composed of coinage, transition metal andgroup 14 elements. Experimental studies based on laser vaporization cluster production, mass
spectrometry, laser spectroscopy, and photofragmentation will be discussed. Further insight incluster functionality is obtained by comparisons with quantum chemical computations, mainly
based on density functional theory.

Friday September 12TH

INV19Clusters as Model Systems for Catalysis
Thorsten M. Bernhardt
Institute of Surface Chemistry and Catalysis, University of Ulm,
Albert-Einstein-Allee 47, 89069 Ulm, Germany
Gas phase metal clusters represent ideal model systems to gain molecular level insight into theenergetics and kinetics of metal-mediated catalytic reactions. In this contribution the idea of metalcluster model systems for catalysis will be illustrated with a particular emphasis put on theimportance of a conceptual understanding gained through these well-defined studies [1].
Furthermore, specific examples from our laboratory will be presented that illustrate the potential ofion trap mass spectrometry (in combination with collaborative first principles calculations) to reveal
pertinent molecular details of important catalytic processes. These examples will cover a wide
variety of reaction systems ranging from the CO combustion catalyzed in car exhaust converters[2] over hydrogen feed gas purification catalysts important to advanced fuel cell technologies [3] tothe water splitting reaction mediated by the manganese oxide cluster complex [4], which is theactive catalytic center of the photosystem II in biological oxygen evolving systems.
Reference(s)[1] S.M. Lang, T.M. Bernhardt, Phys. Chem. Chem. Phys. 14 (2012) 9255.
[2] S.M. Lang, I. Fleischer, T.M. Bernhardt, R.N. Barnett, U. Landman, J. Am. Chem. Soc. 134(2012) 20654.
[3] S.M. Lang, T.M. Bernhardt, M. Krstić, V. Bonačić-Koutecký, Angew. Chem. Int. Ed. 53 (2014)
5467.
[4] S.M. Lang, I. Fleischer, T.M. Bernhardt, R.N. Barnett, U. Landman, Nano Lett. 13 (2013) 5549.

Friday September 12TH

HT23

Stable stoichiometry and chemical reactivity of cluster ions revealed by hightemperature TPD experiments
Fumitaka Mafuné,1 Ken Miyajima,2 and Toshiaki Nagata3
1

Department of Basic Science, School of Arts and Sciences, The University of Tokyo,
Tokyo, Japan

Temperature programmed desorption (TPD) is commonly used in a surface chemistry, whichenables us to identify dissociating species from the surface as a function of a temperature. For gas
phase clusters, challenging experiments have been performed by Bernhardt and his coworkers ina lower temperature than a room temperature for a variety of elements and novel reactions ofclusters with small molecules have been proposed. In the present study, we focused on
developing TPD for the gas phase clusters in a higher temperature, because practically, aconsiderable number of the catalytic reactions of bulk materials are known to proceed at hightemperature.
Cerium oxide is commonly used in a practical catalyst as a catalytic support and a catalytic
promoter as well. It is known that cerium takes both +3 and +4 charge states, so that it tends toadsorb oxygen in an oxygen rich environment, whereas it releases oxygen in an oxygen poor
environment. The propensity relates to oxygen storage capacity of cerium oxide. In the present
study, we examined thermally stable stoichiometry and chemical reactions of the gas phasecerium oxide clusters using TPD method. Cerium oxide cluster ions, CenO2n+x+ (n = 3–10, x = −1
to +2), were prepared in the gas phase by laser ablation of a cerium oxide rod in the presence ofoxygen diluted in He as the carrier gas. The stable stoichiometry of the cluster ions wasinvestigated using a mass spectrometer in combination with TPD. Oxygen molecules were foundto be released from the oxygen-rich clusters, CenO2n+x+(x = 1, 2), and stoichiometric CenO2n-1+

and CenO2n+ were exclusively formed by heating treatment at 573 K as,
CenO2n+x+→ CenO2n+x-2+ + O2 ↑ → CenO2n-4+ + O2 ↑ → …. → CenO2n-1+ and CenO2n+CenO2n-1+ and CenO2n+ species were thus
oxygen-rich clusters consisted of robust
CenO2n-1+

andCenO2n+and weakly boundoxygen atoms. When the stoichiometricclusters were heated further up to ~800 K,
further oxygen-molecule release started tobeobserved.

Thermaldissociation

processes are size-dependent, which relate
to geometrical and electronical structures of
the clusters.

Ce4O7

+

Relative Intensity

found to be thermally stable and the

+

0.8

Ce4O9

(1)
+

Ce4O8

+

Ce4O10

0.6
0.4

0.2
0.0
300

400

500

Temperature (K)Figure 1. TPD plot for Ce4Om+.

600

Friday September 12TH

HT24

Extending the Sizes and Charge States of Polyanionic Metal Clusters
Steffi Bandelow,1 Franklin Martinez,1,2 Gerrit Marx,1 Lutz Schweikhard,1 and Albert Vass1
1

Institute of Physics, Ernst-Moritz-Arndt University Greifswald, Germany

2

present address: Institute of Physics, University of Rostock, Germany

The ClusterTrap setup [1] combines several ion-storage devices for a variety of experimental
studies on metal clusters including collision-induced dissociation, (delayed) photodissociation,
further ionization to higher positive or negative charge states by electron impact or electron
attachment, respectively. All selection, preparation and interaction steps can be performed on
extended time scales up to several seconds. The unique arrangement of two linear radiofrequency
quadrupole (RFQ) ion traps (Paul traps) and an ion-cyclotron-resonance trap (ICR or Penningtrap) allows one to dedicate them with respect to specific functions and optimizations.
In particular, one Paul trap is used for the accumulation of cluster ions from a pulsed laservaporization source and preselection of the cluster size. In the second Paul trap, electrons can be
attached at well-defined energies by use of a “digital” (i.e. rectangular) RF trapping potential [2].
This allows one to study for the first time the energy dependence of electron attachment topolyanionic metal clusters and to determine the heights of their repulsive Coulomb barriers. With arecent replacement of the superconducting magnet, the field strength was increased from B = 5 T
to 12 T. Thus, the electron attachment in the ICR trap was extended to (negative) charge states ashigh as z = -6 for gold and z = -10 for aluminum clusters, respectively. The yields of the charge
states measured as a function of reaction time confirm a sequential electron-attachment process.
Next, we will study polyanion decay induced by laser light. The studies will be performed withrespect to cluster size, charge state and chemical element as well as laser intensity and photon
energy, and also regarding possible delays between photo-interaction and electron detachment orcluster dissociation. Furthermore, it is planned to use multi-reflection time-of-flight mass
spectrometry, recently further developed by us for precision measurements in nuclear physics [3],for high-resolution separation of the (relatively large) polyanionic cluster, and to combine ion-trap
techniques of polyanion production with their investigation by photo-electron spectroscopy.
[1] L. Schweikhard et al., Eur. Phys. J. D 9 (1999) 15; F. Martinez et al., Eur. Phys. J. D 63 (2011)
255; F. Martinez et al., Int. J. Mass Spectrom. 365-366 (2014) 266.
[2] S. Bandelow et al., Int. J. Mass Spectrom. 336 (2013) 47 and 353 (2013) 49.
[3] R.N. Wolf et al., Int. J. Mass Spectrom. 349-350 (2013) 123; F. Wienholtz et al., Nature 498(2013) 346.

Friday September 12TH

HT25

Characterizationof Single-Molecule Magnets
in Isolation
Joseph Fournier,3 Maximilian Gaffga,1 Joachim Hewer,1 Bernd von Issendorff, 4Mark A. Johnson,3 Johannes Lang,1 Tobias Lau,2 Arkadiusz Lawicki,4 Jennifer Meyer,1Gereon Niedner-Schatteburg,1 Akira Terasaki,5 Matthias Tombers,1 Conrad Wolke,3Vicente Zamudio-Bayer,2,4
1

Department of Chemistry, TU Kaiserslautern, Kaiserslautern, Germany
2
3
4

inducedDepartment of Chemistry, Yale University, New Haven, USA

Department of Physics, University Freiburg, Freiburg, Germany

5

X-ray

BESSY, Helmholtz Center, Berlin, Germany

Department of Chemistry, Kyushu University, Fukuoka, Japan
Magnetic

Circular

Dichroism (XMCD) at the L-edge oftransition

metalshas

servedtodetermine the individual spin- andorbital contributions to the magnetic
momentsofisolated

and

mass

selected cluster ions [1,2]. Here, we
present the results of recent XMCD
experimentsonligandstabilized

complexes, so called single-moleculemagnets (SMMs), as e.g. [Mn12O12(OAc)16(H2O)4]("Mn12-acetate").

Isolation experiments confirm bulk
findings and predicted couplings [3].
Infrared Multiple Photon Dissociation (IR-MPD) spectroscopy serves to obtain complementary
information. Such investigations revealed weak and surprisingly strong metal effects alike, e.g. in
the case of lanthanoid variation. These findings are to discuss in the light of ab initio DFT
modelling.
Reference[1] S. Peredkov, M. Neeb, W. Eberhardt, J. Meyer, M. Tombers, H. Kampschulte, GNS; Phys. Rev.
Lett. 107, (2011), 233401[2] M. Niemeyer, K. Hirsch, V. Zamudio-Bayer, A. Langenberg, M. Vogel, M. Kossick, C. Ebrecht,
K. Egashira, A. Terasaki, T. Moller, B. v. Issendorff, and J. T. Lau; Phys. Rev. Lett. 108, (2012),
057201[3] M. Mannini, P. Sainctavit, R. Sessoli, C. Cartier dit Moulin, F. Pineider, M.-A. Arrio, A.
Cornia, and D. Gatteschi, Chem. Eur. J. 14, (2008), 7530

Friday September 12TH

HT26

Spin orientation in isolated magnetic nanoalloys – topology, dielectric andmagnetic properties of manganese doped tin-clusters Mn/SnN
Urban Rohrmann,1 Peter Schwerdtfeger2 and Rolf Schäfer1
1
2

Department of Chemistry, Technical University of Darmstadt, Darmstadt, Germany

Centre for Theoretical Chemistry and Physics, Massey University, Albany, New Zealand

Molecular beam deflection experiments in inhomogeneous electric and magnetic fields (Stark- andStern-Gerlach experiment, respectively) in combination with density functional theory (DFT) allow
to study systematically the impact of molecular topology on the magnetic response of isolated
nanoalloyed clusters. In Stark-experiments the dielectric response of the clusters is measured.
The electric dipole moment and polarizability are sensitive probes for the topology of theclusters.[1] This allows to identify the molecular geometries by matching experimental observations
with molecular dynamics simulations of the clusters, based on our DFT studies. The
experimentally verified molecular structure (in general the lowest energy isomer in thecomputational studies) then is considered to investigate the correlation with the magnetic
response measured in Stern-Gerlach experiments.
The clusters are generated in a laser ablation source with cryogenically cooled nozzle in order tostudy the influence of thermal excitations of the clusters on the magnetic response. The spatial
distribution (beam profile) of the vibrationally excited clusters is exclusively shifted in the directionof the field gradient with vanishing broadening of the beam profile. This reflects a vibrationallyinduced spin orientation process.[2] The magnetic dipole moments are extracted from the shift ofthe beam profiles and compare very well to the spin-only magnetic dipole moment expected forthe lowest energy spin isomers found computationally.
At very low nozzle temperature a large fraction of each cluster species is at the vibrational groundstate and the magnetic response depends critically on the composition / topology of the cluster.
Mn@Sn12 has been identified as a true paramagnetic superatom, with spatially quantized spin
angular momentum.[2] With one exception (Mn@Sn14) the remaining clusters do not show such
response due to the reduced symmetry molecular environment. This is interpreted in terms ofadiabatic magnetization, induced by avoided crossings among Zeeman levels.[3]Reference(s)[1] S. Heiles, R. Schäfer, Dielectric Properties of Isolated Clusters (Springer, 2014).
[2] U. Rohrmann, R. Schäfer, Phys. Rev. Lett. 111, 133401 (2013).
[3] X. Xu, S. Yin, R. Moro, W. A. de Heer, Phys. Rev. Lett. 95, 237209 (2005).

POSTER SESSION A
September 9th, Tuesday
16:30 - 18:30
Spectroscopy and dynamics
Electronic structure and quantum effects
Biotechnological and medical applications: imaging and sensors
Structure and thermodynamics
Reactivity and catalysis

A1-A17
A18-A36
A37-A41
A42-A65
A66-A88

A1

A2

A3

A4

A5

A6

A7

A8

A9
A10

A11

First-Principles Study of Excited State Evolution in a Protected Gold
Complex
Olga Lopez-Acevedo, Ari Ojanperä, Martti Puska ; Aalto University
Optical properties and structures of isolated gold-silver nanoalloys frommolecular beam photodissociation spectroscopy
A. Shayeghi1, D. A. Götz1, R. L. Johnston2, R. Schäfer1 ; 1 Technische Universität
Darmstadt, 2 University of Birmingham
Fluorescent oxidized Si nanoclusters and reversible interactions withsolvent
Hanieh Yazdanfar, Mike J. McNally, Gediminas Galini, Mark Watkins, Klaus vonHaeften ; University of Leicester
Single-shot imaging of giant Xe clusters with X-ray free-electron laser
T. Nishiyama1, C. Bostedt2, K. R. Ferguson2, C. Hutchison1, K. Nagaya1,3, H.
Fukuzawa3,4, K. Motomura4, S. Wada3,5, T. Sakai1, K. Matsuami1, T. Tachibana4,
Y. Ito4, W. Q. Xu4, S. Mondal4, T. Umemoto5, C. Nicolas6, C. Miron6, T.
Kameshima7, Y. Joti7, K. Tono7, T. Hatsui3, M. Yabashi3, K. Ueda3,4, M. Yao1 ; 1
Kyoto University, 2 SLAC National Accelerator Laboratory, 3 RIKEN SPring-8
Center, 4 Tohoku University, 5 Hiroshima University, 6 Synchrotron SOLEIL,
L'Orme des Merisiers, 7 JASRI
Ultrafast dynamics in single clusters captured with time-resolved x-ray
imaging
D. Rupp1, M. Adolph1, L. Flückiger1, T. Gorkhover1,2, M. Krikunova1, J.-P. Müller1,
M. Müller1, M. Sauppe1, D. Wolter1, S. Schorb1,2, S. Düsterer4, R. Treusch4, C.
Bostedt2,3, T. Möller1 ; 1 IOAP, Technische Universität Berlin, 2 LCLS at SLAC
National Accelerator Laboratory, 3 Stanford University and SLAC, 4 FLASH at
DESY
Momentum mapping of fragment ions generated upon Coulomb explosionsof dichloroethylene isomers in intense laser fields
Yoriko Wada1, Hiroshi Akagi2, Ryuji Itakura2, Tomonari Wakabayashi1, Takayuki
Kumada2 ; 1 Kindai University, 2 Japan Atomic Energy Agency
Vibrational Spectroscopy of Monolayer Protected Gold Clusters: A Close
Look at the Au-S Interface
Birte Varnholt, Patric Oulevey, Igor Dolamic, Thomas Bürgi ; University ofGenevaVibrational spectroscopy of Au-nanocluster single crystals
Jaakko Koivisto, Kirsi Salorinne, Satu Mustalahti, Tanja Lahtinen, Sami Malola,
Hannu Häkkinen, Mika Pettersson ; University of Jyväskylä
Two-color IR-UV spectroscopy of NbnCm clusters
Valeriy Chernyy, Joost Bakker, Andrei Kirilyuk ; Radboud University Nijmegen
Comparative study of ultrafast relaxation dynamics of Au144(C2H4Ph)60 and
Au102(pMBA)44 nanoclusters by using mid-IR transient absorption
spectroscopy
Satu Mustalahti, Pasi Myllyperkiö, Tanja Lahtinen, Sami Malola, Kirsi Salorinn,
Jaakko Koivisto, Hannu Häkkinen, Mika Pettersson ; University of Jyväskylä
Characterization of counter ions in solutions using thiol molecules
adsorbed on silver nanoparticles
Saori Handa, Yingying Yu, Masayuki Futamata ; Saitama University

A12
A13

A14

A15

A16

A17

A18

A19

A20

A21

A22

Highly-sensitive gap mode Raman spectroscopy on various substrates
Maho Ishikura, Hiroki Suzuki, Masayuki Futamata ; Saitama University
In-situ produced BiOx nanoparticles: Studied in a beam and as depositedby photoelectron spectroscopy
Mikko-Heikki Mikkelä1, Maxim Tchaplyguine1, Chaofan Zhang2, Tomas
Andersson2, Erik Mårsell1, Olle Björneholm2 ; 1 Lund University, 2 Uppsala
University
Photofragment-ion imaging from mass-selected cluster ions using alinear-type tandem reflectron
Kenichi Okutsu, Kenichiro Yamazaki, Keijiro Ohshimo, Fuminori Misaizu ;Tohoku University
Time Resolved Study of EUV-FEL Triggered Nano-Plasma of Rare-Gas
Clusters
K. Nagaya1,2, T. Sakai1, T. Nishiyama1, K. Matsunami1, S. Yase1, M. Yao1, H.
Fukuzawa2,3, K. Motomura3, T. Tachibana3, S. Mondal3, K. Ueda2,3, S. Wada2,4, H.
Hayashita4, N. Saito2,5, T. Togashi2,6, M. Nagasono2, M. Yabashi2 ; 1 Kyoto
University, 2 RIKEN SPring-8 Center, 3 Tohoku University, 4Hiroshima University,
5
NMIJ, AIST, 6 JASRI
X-ray absorption spectroscopy of size-selected cerium oxide clusters
Tetsuichiro Hayakawa1, Masashi Arakawa2, Shun Sarugaku2, Kota Ando2,
Kenichiro Tobita2, Tomonori Ito2, Kazuhiro Egashira1, Akira Terasaki2,3 ; 1 East
Tokyo Laboratory, Genesis Research Institute, Inc., 2 Kyushu University, 3 Toyota
Technological Institute
Photodepletion spectroscopy of silver cluster cations in atemperature-controlled ion trap
Tomonori Ito, Kenichiro Tobita, Masashi Arakawa, Akira Terasaki ; Kyushu
University
Geometry, Electronic, and Magnetic properties as well as selective O2 andCO adsorption on AunRhm clusters
Marcela .R. Beltrán, Fernando. Buendía ; Universidad Nacional Autónoma deMéxico, Instituto de Investigaciones en Materiales
AB INITIO STUDY OF CATIONIC, ANIONIC AND NEUTRAL AunRhm
CLUSTERS
Fernando Buendía1, Marcela R. Beltrán1 ; 1Universidad Nacional Autónoma deMéxico, Instituto de Investigaciones en Materiales
Electronic and optical properties of hetero-assembled endohedral
superatomic clusters
Takeshi Iwasa1,2, Atsushi Nakajima1,2 ; 1 Nakajima Designer Nanocluster
Assembly project, JST-ERATO, 2 Keio University
Electronic structure of rare-earth clusters: from number of 4f-electrons tomagnetism
Lars Peters1, Saurabh Ghosh2, Igor di Marco2, Biplab Sanyal2, Anna Delin2, Misha
Litcarev2, Theo Rasing1, Andrei Kirilyuk1, Olle Eriksson2, Mikhail Katsnelson1 ; 1
Radboud University Nijmegen, 2 Uppsala University
Coexistence of Insulating and Metallic States, and other Unusual Electronicand Magnetic Properties of Pure and Doped Zinc Clusters
Andrés Aguado1, Andrés Vega1, Alexandre Lebon2, Bernd von Issendorff3 ; 1
Valladolid University, 2Brest University, 3 Universität Freiburg

A23

A24

A25

A26

A27

A28

A29

A30

A31

A32

A33

A34

Probing of an Adsorbate-Specific Excited State on an Organic Insulating
Surface by Two-Photon Photoemission Spectroscopy
Masahiro Shibuta1, Naoyuki Hirata1,2, Toyoaki Eguchi1,2, Atsushi Nakajima1,2 ; 1
Keio University, 2 JST, ERATO, Nakajima Designer Nanocluster Assembly
Project
Full relativistic calculations of electronic and magnetic properties of small
cationic and neutral bismuth clusters
Josef Anton1, and Timo Jacob1, Arne Rosen2 ; 1 University of Ulm, 2University ofGothenburg
Phase Transition Behavior and Ionic Conductivity of Small Silver Iodide
Quantum Dots
Takayuki Yamamoto1, Hirokazu Kobayashi1,2, Yoshiki Kubota3, Hiroshi
Kitagawa1,2 ; 1 Kyoto University, CREST, JST, 3 Osaka Prefecture University
A new structural model for Al23– magic cluster: A face-sharingbi-icosahedral motif
Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1The University of Tokyo, 2 Kyoto
University
Non-spherical gold clusters with the lowest-energy intense absorptions:strong correlation between geometric and electronic structures
Yukatsu Shichibu1,2, Mingzhe Zhang2, Katsuaki Konishi1,2 ; 1 Hokkaido University,
2
Hokkaido University
Density functional theory study on hydrogen absorption properties ofnano-sized transition metal clusters (1): difference between Pd/Pt bulk andtheir clusters
Aya Matsuda, Hirotoshi Mori ; Ochanomizu University
Density functional theory study on hydrogen absorption properties ofnano-sized transition metal clusters (2): dependency on composition andinternal structures
Kasumi Miyazaki, Aya Matsuda, Hirotoshi Mori ; Ochanomizu University
Electronic shell closure of Al13 by electron donation from PVP
Tomomi Watanabe1,2, Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1 The Universityof Tokyo, 2 Kyoto University
Precise Separation of Metal Clusters Protected by Two-Types of Thiolate
Ligands
Yoshiki Niihori, Miku Matsuzaki, Chihiro Uchida, Yuichi Negishi ; Tokyo
University of Science
Ultrafast photoelectron spectroscopy of metal clusters supported on MgOand Si substrates
Florian Knall1, Mihai E. Vaida1, Thorsten M. Bernhardt1, Hisato Yasumatsu2,
Nobuyuki Fukui3 ; 1 University of Ulm, 2 Toyota Technological Institute;
3
East Tokyo Laboratory, Genesis Research Institute, Inc.
Graphene-supported metal clusters: Well-defined nanostructures for theinvestigation of photo-induced processes
Kira Jochmann, Thorsten M. Bernhardt ; University of Ulm
Properties of designed small gallium-nitride clusters
Tibor Höltzl ; Furukawa Electric Institute of Technology

A35

A36

A37

A38

A39

A40

A41

A42
A43

A44

A45

A46

Stabilization of Magic-Numbered Au25(SR)18 Cluster
Wataru Kurashige1, Masaki Yamaguchi1, Katsuyuki Nobusada2, Yuichi Negishi1 ;1Tokyo University of Science, 2 Institute for Molecular Science
Theoretical Study on the Ln Dependence of Ln(COT)2 Photoelectron
SpectraErika Nakajo, Tomohide Masuda, Satoshi Yabushita ; Keio University
Functionalized Gold Nanoclusters as Site-Specific Labels for Imaging ofEnteroviruses
Kirsi Salorinne1, Varpu Marjomäki2, Tanja Lahtinen1, Mari Martikainen2, Jaakko
Koivisto1, Sami Malola3, Mika Pettersson1, Hannu Häkkinen1,3 ; 1 University of
Jyväskylä, 2 University of Jyväskylä, 3 University of Jyväskylä
Metal nanoparticle modified electrochemical electrodes for nonenzymehydrogen peroxide sensing
Jue Wang, Xuejiao Chen, Kaiming Liao, Guanghou Wang, Min Han ; Nanjing
University
Gold Nanorod Assisted Laser Desorption/Ionization of Oligopeptides
Masanori Fujii1, Naotoshi Nakashima1,2,3,Yasuro Niidome1,2,4 ; 1 Kyushu
University, 2 Kyushu University, 3 CREST, 4 Kagoshima University (Present
Affiliation)
Spontaneous Formation of Gold Glyconanoparticles by Direct Reaction of
ω-Glycosilated Alkylsulfanylanilines and HAuCl4
Ryuich Takegawa, Satoaki Onitsuka, Toshiyuki Hamada, Jun-ich Kurawaki,
Hiroaki Okamura ; Kagoshima University
Nanopore devices for rapid structural analysis of Nanomaterials
Sou Ryuzaki1, Masateru Taniguchi2, Koichi Okamoto1, Kaoru Tamada1 ; 1
Kyushu University, 2 Osaka University
Silver acetylide nano helical structure induced by impurities
Shota Ito, Yoshikiyo Hatakeyama, Ken Judai ; Nihon University
Rapid cooling of isolated small carbon cluster anions
Takeshi Furukawa1, Naoko Kono1, Gen Ito1, Jun Matsumoto1, Hajime Tanuma1,
Toshiyuki Azuma2, Klavs Hansen3, Haruo Shiromaru2 ; 1 Tokyo Metropolitan
University, 2 Atomic, Molecular and Optical Physics Laboratory, RIKEN, 3
University of Gothenburg
Radiative cooling of laser-heated niobium clusters
Klavs Hansen1, Yejun Li2, Vladimir Kaydashev2, Ewald Janssens2 ; 1 University ofGothenburg, 2 KU Leuven
Adsorbing carbon dioxide on fullerenes at 0.37K under the influence of
charge: a mass spectrometric and molecular dynamics/DFT study
Stefan Ralser1, Johannes Postler1, Alexander Kaiser1, M. Probst1, S. Denifl1,
Diethard K. Böhme2, Paul Scheier1 ; 1 Universität Innsbruck, 2 York University
Entropy-driven isomer switching in Fe+(H2O)n probed with IR spectroscopy
and free-energy calculations
Kazuhiko Ohashi1, Jun Sasaki1, Gun Yamamoto1, Ken Judai2, Nobuyuki Nishi2,
Hiroshi Sekiya1 ; 1 Kyushu University, 2 Institute for Molecular Science

A47

A48

A49

A50

A51
A52
A53
A54

A55

A56

A57
A58

A59

Syntheses of Au@PdAg and Au@PdAg@Ag core–shell Nnanorods throughdistortion induced alloying between Pd shells and Ag atoms over Au
nanorods
Masaharu Tsuji , Koichi Takemura, Chihiro Shiraishi, Keiko Uto, Atsuhiko
Yajima3, Masashi Hattori, Takeshi Daio ; Kyushu University
Ligand-protected gold clusters with novel interfacial structures
Prasenjit Maity1, Jun-ichi Nishigaki1, Tatsuya Tsukuda1,2 ; 1 The University ofTokyo, 2 Kyoto University
Isolation and properties of chiral Pd2Au36(SR)24 cluster
Noelia Barrabés1, Bei Zhang1, Houhua Li2, Kaziz Sameh3, Dawid Wodka1,
Clément Mazet2, Jordi Llorca4, Thomas Bürgi1 ; 1 University of Geneva, 2
University of Geneva, 3 Superior National School of engineers of Tunis, 4Technical University of Catalonia
Alternate shell structure in Fe-Co nanoparticles
Bheema Lingam Chittari1, Vijay Kumar1,2 ; 1Dr. Vijay Kumar Foundation(VKF),
2
Shiv Nadar University
Bond Length Analysis of Au Nanoparticles Synthesized in Ionic Liquids
Yoshikiyo Hatakeyama1, Kiyotaka Asakura2, Ken Judai1, Keiko Nishikawa3 ;1Nihon University, 2 Hokkaido University, 3 Chiba University
withdraw
Generation of a liquid droplet in a vacuum
Kota Ando, Masashi Arakawa, Akira Terasaki ; Kyushu University
Vibrational properties of metal nanoparticles: From structural dependence
to intrinsic damping
Huziel E. Sauceda1, Israel Acuña-Galván2,3, Ignacio L. Garzón1 ; 1 Universidad
Nacional Autónoma de México, 2 Centro Universitario UAEM Zumpango, 3 UAEH,
HidalgoAn incorporation of the concept of a bifurcation pathway to global reaction
route mapping analyses: An application to Au5 cluster
Tetsuya Taketsugu1,2, Yu Harabuchi1, Yuriko Ono1, Satoshi Maeda1,2 ; 1
Hokkaido University, 2 Kyoto University
Stability and morphology of platinum cluster supported on silicon
substrate in heating cycles
Nobuyuki Fukui1, Hisato Yasumatsu2 ; 1 East Tokyo Laboratory, Genesis
Research Institute, Inc., 2 Cluster Research Laboratory, Toyota Technological
Institute
Synthesis of a novel [core+exo]-type heptanuclear gold cluster
Mingzhe Zhang, Yukatsu Shichibu, Katsuaki Konishi ; Hokkaido University
Exploration on Magic Binary Nanoclusters Consisting of Silicon-Transition
Metal Atoms by Reaction with Molecular Oxygen
Yoshito Sugawara1, Tomomi Nagase1, Hironori Tsunoyama1,2, Atsushi
Nakajima1,2 ; 1 Keio University, 2 Nakajima Designer Nanocluster Assembly
Project, JST-ERATO
Preparation and redispersible solidification of monodisperse CdSe
nanoparticles capped with cysteine in water
Yasuto Noda, Isao Sawakami, Takuya Kurihara, K. Takegoshi ; Kyoto University

A60

A61

A62

A63
A64

A65

A66

A67

A68

A69

A70

Low temperature XAFS study of thiolate-protected Au clusters
Seiji Yamazoe1,2, Shinjiro Takano1, Wataru Kurashige3, Yuichi Negishi3, Tatsuya
Tsukuda1,2 ; 1 The University of Tokyo, 2 Kyoto University, 3 Tokyo University of
Science
Ionic cluster formation using an ion drift-tube with selected-ion injection Measurement of thermodynamic quantities for H3O+ Hydrate
Yoichi Nakai1, Hiroshi Hidaka2, Naoki Watanabe2, Takao M. Kojima3 ; 1 RIKEN
Nishina Center for Accelerator-Based Science, 2 Hokkaido University, 3 Atomic
Physics Laboratory, RIKEN
Nanoparticle formation by interaction between laser ablated plume andshock waves
Eri Ueno1, Naoaki Fukuda2, Hiroshi Fukuoka3, Minoru Yaga4, Ikurou Umezu5, Min
Han6, Toshio Takiya1 ; 1 Hitachi Zosen Corporation, 2 Kyoto University, 3 Nara
National College of Technology, 4 University of the Ryukyus, 5 Konan University,
6
Nanjing University
Structures of small silicon-doped gold cluster cations
Jun Miyawaki, Ko-ichi Sugawara ; AIST
Location of dopant M (M = Pd, Ag, Cu) within Au25-xMx(SR)18 studied by
XAFS
Seiji Yamazoe1,2, Wataru Kurashige3, Katsuyuki Nobusada2,4, Yuichi Negishi3 ,Tatsuya Tsukuda1,2 ; 1 The University of Tokyo, 2 Kyoto University, 3 Tokyo
University of Science, 4 Institute for Molecular Science
Space-Focusing of Spatially Spread Ions in Time-of-Flight Mass
Spectrometer
Shun Sarugaku, Ryohei Murakami, Masashi Arakawa, Akira Terasaki ; Kyushu
University
Understanding and designing nanoalloys for clean energy applications by
first principles calculations
Daojian Cheng ; Beijing University of Chemical Technology
Conformations of Biomolecular Ions Probed by Proton Transfer Reactions
at Various Temperature
Shinji Nonose, Minami Kawashima, Hideo Isono ; Yokohama City University
Reactions of Copper Cluster Oxide Anions with Nitric Oxide: Enhancementof Adsorption by Partial Oxidation
Shinichi Hirabayashi1, Masahiko Ichihashi2 ; 1 East Tokyo Laboratory, Genesis
Research Institute, Inc., 2 Toyota Technological InstituteVibrational Spectroscopy of Aluminum Oxide Cluster Anions: Structure
and Reactivity
Xiaowei Song1,2, Matias R. Fagiani1,2, Florian A. Bischoff3, Wieland Schöllkopf1,
Sandy Gewinner1, Joachim Sauer3, Knut R. Asmis1,2 ; 1 Fritz-Haber-Institut der
Max-Planck-Gesellschaft, 2 Universität Leipzig, 3 Humboldt-Universität Berlin
Homogeneous deposition of size-selected clusters using Lissajous
scanning method
Atsushi Beniya1, Noritake Isomura1, Hirohito Hirata2, Yoshihide Watanabe1 ; 1
Toyota Central R&D Labs., Inc., 2 Toyota Motor Corporation

A71

A72

A73

A74

A75

A76

A77

A78

A79

A80
A81
A82

A83

Time-of-flight mass spectrometry for reaction product detection inheterogeneous catalysis
A. Winbauer, M. Tschurl, J. Kiermaier, U. Boesl, U. Heiz ; Technische Universität
MünchenH and O adsorption on Fe13Pt42 core-shell nanoparticle
Bheema Lingam Chittari1, Vijay Kumar1,2 ; 1Dr. Vijay Kumar Foundation(VKF),
2
Shiv Nadar University
Au38(SR)24 cluster for oxidation catalysis
Bei Zhang1, Houhua Li2, Miguel A.G. Hevia3, Kaziz Sameh4, Dawid Wodka1,
Clements Mazet2, Thomas Bürgi1, Noelia Barrabés1 ; 1 University of Geneva, 2
University of Geneva, 3 ICIQ, 4 Superior National School of Engineers of Tunis
A new scalable Matrix Assembly Cluster Source (MACS) operating inreflection mode.
William D Terry, Feng Yin, Jian Liu, Lu Cao, Richard E Palmer ; University ofBirmingham
Theoretical study of the dehydrogenation of isopropanol on Ni13 cluster
supported on Θ-Al2O3(010) surface
Andrey Lyalin1, Tetsuya Taketsugu1,2 ; 1 Kyoto University, 2 Hokkaido University
Chemical Reactivity of Rhodium and Copper-doped Rhodium Neutral
Clusters
Masato Takenouchi, Ken Miyajima, Fumitaka Mafuné ; The University of Tokyo
Reduction of N2 on Pd surfaces at low temperatures
Junichi Murakami1, Masayuki Futamata1, Yukimichi Nakao2, Shin Horiuchi2,
Kyoko Bando2, Umpei Nagashima2, Kazuki Yoshimura2 ; 1Saitama University,
2
AIST,
Automated prediction of pathways for single bond activations on small
gold clusters: A case study of H2 dissociation on neutral and charged Aunm(n = 1-12, m = 0, ±1)
Min Gao1, Andrey Lyalin2, Satoshi Maeda1,2, Tetsuya Taketsugu1,2 ; 1 Hokkaido
University, 2 Kyoto University
Preparation and catalytic application of supported silver clusters
Masaru Urushizaki1, Shinjiro Takano1, Seiji Yamazoe1,2, Kiichirou Koyasu1,2,
Tatsuya Tsukuda1,2 ; 1 The University of Tokyo, 2 Kyoto University
A Highly Practical and Reusable Zinc Catalyst for Transesterification
Daiki Nakatake, Yuki Yokote, Ryo Yazaki, Takashi Ohshima ; Kyushu University
Thermal stability and reactivity of manganese oxide clusters
Kohei Koyama, Ken Miyajima, Fumitaka Mafuné ; The University of Tokyo
Studies on chemical reactions of transition metal clusters with oxygen byusing FT-ICR mass spectrometer
Yuta Tobari1, Kazuki Ogasawara2, Yoshinori Sato2, Makoto Saito2 , Shohei
Chiashi2, Shigeo Maruyama2 , Toshiki Sugai1 ; 1 Toho University, 2 The Universityof TokyoFirst-principle study of small nickel cluster structure and hydrogendissociation on nickel dimer
Pham Thi Nu, Ohno Kaoru : Yokohama National University

A84

A85
A86
A87

A88

Clusters on La-Ni Mixed Oxides and its Catalytic Performance for
Isomerization of Allylic Alcohols to Saturated Aldehydes
Tamao Ishida1,4, Jun Aimoto1, Akiyuki Hamasaki1, Hironori Ohashi1, Tetsuo
Honma2, Takushi Yokoyama1, Kohei Sakata3, Mitsutaka Okumura3, Makoto
Tokunaga,1 ; 1 Kyushu University, 2 JASRI/SPring-8, 3 Osaka University, 4 Tokyo
Metropolitan University
withdraw
Release of Oxygen from Copper Oxide Cluster Ions by Heat
Ken Miyajima, Keisuke Morita, Fumitaka Mafuné ; The University of Tokyo
Regenerative synthesis of copper nanoparticles on TiO2 nanoparticles byphotoreduction
Naoki Nishida, Takuya Aoki, Hideki Tanaka ; Chuo University
Stoichiometry of cationic and anionic vanadium oxide clusters analyzed byion mobility-mass spectrometry
Jenna W.J. Wu, Ryoichi Moriyama, Hiroshi Tahara, Keijiro Ohshimo, Fuminori
Misaizu ; Tohoku University

A1

Spectroscopy and dynamics

First-Principles Study of Excited State Evolution in a Protected Gold Complex
Olga Lopez-Acevedo,1 Ari Ojanperä,1 and Martti Puska1
1

COMP Centre of Excellence, Department of Applied Physics, Aalto University, P.O. Box 11100,
00076 Aalto, Finland

We

have

studiedthephotoexcitation

dynamics

oftheprotected

goldcomplex

Au2(SCH3)(PH3)2+1 [1]. In our calculations, we used a combination of the Delta
Self-Consistent-Field method, Ehrenfest dynamics, and the time-dependent density functional
theory. Our simulations provide insight into two types of mechanisms that can be tuned toenhance the photoluminescence of protected clusters in solution. Using Bader charge analysis we
found that a charge transfer process between ligands appears upon excitation and that a chargetransfer from the core toward the ligands takes place during the first tens of femtoseconds of thenonadibatic evolution. A later, hundreds of femtoseconds long reverse charge transfer process
results in an asymmetric distribution of charge between the metal atoms. The charge redistribution
and the oscillator strength of the excited-to-ground-state stimulated transition are coupled in bothmechanisms. These results will help the understanding of emission properties of larger and more
complex protected clusters.

Reference[1] A. Ojanperä, M. Puska and O. Lopez-Acevedo, J. Phys. Chem. C 117 (2013) page. 11837

Spectroscopy and dynamics

A2

Optical properties and structures of isolated gold-silver nanoalloys frommolecular beam photodissociation spectroscopy
A. Shayeghi,1 D. A. Götz,1 R. L. Johnston,2 and R. Schäfer1
1

Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische
Universität Darmstadt, Alarich-Weiss-Str. 8, 64287 Darmstadt, Germany

2

School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT,
United Kingdom

Gold-silver nanoalloys have attracted much attention in the past, especially due to their very
interesting optical properties [1]. Here, we present experimental and theoretical studies of opticalabsorption spectra of AgNAuM+ (3 ≤ N+M ≤ 5) clusters in the photon energy range ħ= 1.9 - 4.4 eV
for the ﬁrst time. The clusters are produced by pulsed laser vaporization and detected using
time-of-ﬂight mass spectrometry. The optical response is probed by photodissociation using atunable ns-laser pulse from an optical parametric oscillator. Absorption spectra are recorded bymonitoring the ion signal depletion upon photon absorption, providing a lower limit to absolute
photodissociation cross sections. The spectra are compared to optical response calculations in theframework of long-range corrected time-dependent density functional theory, which has beenshown to perform well for gold-silver tetramer clusters (N+M = 4) in previous studies [2, 3].
The cluster geometries used in excited state calculations are obtained by an extensive potential
energy surface search employing the Birmingham Cluster Genetic Algorithm coupled with density
functional theory [4, 5]. We also intend to perform geometry optimizations and subsequent excitedstate calculations based on coupled cluster theory. These combined theoretical and experimental
studies pave the way for a deeper understanding of the gold-silver nanoalloy clusters electronic
structure.
Reference(s)[1] R. Ferrando, J. Jellinek, and R. L. Johnston, Chem. Rev. 108 (2008) 845.
[2] A. Shayeghi, R. L. Johnston, and R. Schäfer, Phys. Chem. Chem. Phys. 15 (2013) 19715.
[3] A. Shayeghi, C. J. Heard, R. L. Johnston, and R. Schäfer, J. Chem. Phys. 140 (2014) 054312.
[4] S. Heiles, A. J. Logsdail, R. Schäfer, and R. L. Johnston, Nanoscale 4 (2012) 1109.
[5] R. L. Johnston, Dalton Transactions, (2003) 4193.

A3

Spectroscopy and dynamics

Fluorescent oxidized Si nanoclusters and reversible interactions with solvent
Hanieh Yazdanfar,1 Mike J. McNally,1 Gediminas Galinis,1 Mark Watkins,1 and Klaus von Haeften1
1

Department of Physics and Astronomy, University of Leicester, UK

Fluorescent silicon nanoclusters have been produced by a novel method developed in our group.
The process involves the co-deposition of the silicon particles and a liquid jet. A sample of several
millilitres, containing clusters 1nm in size, is produced in only few minutes [1, 2]. Aging experimentproves that these fluorescent particles have not agglomerated and remained stable in the solution
after several years. Their fluorescence intensity has not changed in 3 years. X-ray photo emission
spectroscopy and attenuated total reflection was used to analyse the chemical composition of thematerials. The results revealed that all the silicon was oxidized. Hence, the infrared absorption
bands were attributed to SiOH, SiH, and SiOx compounds.
Samples can be produced in different solvents such as water, ethanol, and isopropanol. The
wavelength of fluorescence bands depends on the dipole moments of the solvents, the larger the
dipole moments, the more the shift to longer wavelengths. Distillation experiments show that theposition of fluorescent peaks of the nanoclusters not only depends on chemical reactions between
silicon particles and the liquid jet during growth, but also on the solvents that nanoclusters havebeen kept in. This is inferred from measurements performed after the sample completely dried out
and dissolved in another solvent. The sequence was repeated several times using water andethanol as solvents. Figure 1 shows spectra after four reversible distillation cycles. The results
show that the peak position shifts with change of the solvent due to differences in the dipole
moments. Lifetime Measurements show that the dipole moment of solvents also influences the life
time of nanoclusters as the decay time is observed to vary from 3.7 to 5.6 ns.

Figure 1. Fluorescence spectra of silicon nano clusters in ethanol
and water. The solid symbols show fluorescence spectra forsilicon clusters in ethanol, with the peak position at 320 nm. As the
sample dried and dissolved into the water, the peak position
shifted to 440 nm as is seen in the empty symbols.

Figure2. Lifetime of silicon nanoparticles in water (top),ethanol (middle), and isopropanol (bottom).

References[1] G. Torricelli, A. Akraiam, and K. von Haeften, Nanotechnology 22, 315711 (2011).
[2] G. Galinis, H. Yazdanfar, M. Bayliss, M. Watkins, and K. von Haeften, J. Nanopart. Res. 14,
1019 (2012).

Spectroscopy and dynamics

A4

Single-shot imaging of giant Xe clusters with X-ray free-electron laser
T. Nishiyama1, C. Bostedt2, K. R. Ferguson2, C. Hutchison1, K. Nagaya1,3, H. Fukuzawa3,4,
K. Motomura4, S. Wada3,5, T. Sakai1, K. Matsuami1, T. Tachibana4, Y. Ito4, W. Q. Xu4, S. Mondal4,
T. Umemoto5, C. Nicolas6, C. Miron6, T. Kameshima7, Y. Joti7, K. Tono7, T. Hatsui3, M. Yabashi3,
K. Ueda3,4, and M. Yao1
1

2

Department of Physics, Kyoto University, Kyoto, JapanSLAC National Accelerator Laboratory, United States of America
3

4

RIKEN SPring-8 Center, Hyogo, Japan

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan
5

Department of Physical Science, Hiroshima University, Hiroshima, Japan

6

Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, Cedex, France

7

Japan Synchrotron Radiation Research Institute (JASRI), Hyogo, Japan

X-ray free-electron laser (X-FEL) delivers spatially coherent and extremely intense x-ray pulses,
which enables us to study three-dimensional structural analysis of nanoscale single particles. In
particular, combination of x-ray scattering and other techniques such as ion time-of-flight (TOF)
spectroscopy is expected to provide information on physical properties in connection with structure.
This method is especially useful for clusters, whose formation through aggregation can produce
many structural isomers.
We report here the results of the small-angle x-ray scattering of sub-micron xenon (Xe) clusters.
The experiment was carried out at the experimental hutch 3 of the beamline 3 of SACLA. The
power density of X-FEL was around 1017 W/cm2. The wavelength was 2.2Å (5.5 keV) and thepulse width was 10 femtoseconds.
We observed a clear diffraction image from a single sub-micron Xe cluster even with a single
X-FEL pulse. We also obtained fluorescence photons and ion TOF spectra from ionized clusters,
and they had strong correlation with the diffraction images.
This study was supported by the X-ray Free Electron Laser Utilization Research Project and the
X-ray Free Electron Laser Priority Strategy Program of the MEXT, by JSPS, by the Proposal
Program of SACLA Experimental Instruments of RIKEN, and by the IMRAM project.

Spectroscopy and dynamics

A5

Ultrafast dynamics in single clusters captured
with time-resolved x-ray imaging
D. Rupp,1 M. Adolph,1 L. Flückiger,1 T, Gorkhover,1,2 M. Krikunova,1 J.-P. Müller,1 M. Müller,1 M.
Sauppe,1 D. Wolter,1 S. Schorb,1,2 S. Düsterer,4 R. Treusch,4 C. Bostedt,2,3 and T. Möller1
1

IOAP, Technische Universität Berlin, Germany

2

LCLS at SLAC National Accelerator Laboratory, Menlo Park, USA

3

PULSE Institute, Stanford University and SLAC, Menlo Park, USA
4

FLASH at DESY, Hamburg, Germany

Extremely bright and ultrashort x-ray pulses from free-electron lasers have initiated new fields ofresearch. One of the pioneering projects is capturing molecular movies, i.e. imaging of single
molecules and ultrafast molecular processes with atomic resolution in time and space. The mostchallenging task is to record a scattering image from a single molecule or cluster before electronicchanges and ionic motion within the molecule blur the scattering pattern. In order to approach thisgoal, we strive towards a profound understanding of ultrafast radiation damage.
Atomic clusters have been successfully used as ideal model systems to study laser-matterinteraction. We have recently developed single cluster imaging and simultaneous ion
spectroscopy as a novel method delivering unprecedented insight into the FEL-induced ionizationand plasma dynamics [1, 2]. Knowing the size of the cluster and the FEL exposure power densityfrom the scattering patterns allows for experiments with extremely well defined initial conditions.
In recent experiments at the FLASH-FEL single large xenon clusters were irradiated by intense
soft x-ray pulses. The scattering images of the single clusters revealed the built-up of an
inhomogeneous, shell structured, highly charged nanoplasma. The ion spectra of the same, size
selected clusters indicate that after the interaction with the pulse, the outermost shells of thecluster blast off while the most part of the dense cluster plasma – though transiently highly
charged – recombines to neutral atoms. In time-resolved experiments using an infrared
pump-pulse, we could even capture unprecedented speckle-type patterns nanoseconds after
photon exposure which we interpret as the signature of a neutral, slowly expanding gas ball.
In order to create an actual movie from non-reproducible, grown particles such as clusters, theinitial structure has to be known. Therefore as a next step a novel setup, the “X-ray Movie
Camera”, with a multilayer-based split-and-delay unit for x-ray double-pulses up to 500 ps delay isunder construction. Using a novel detector design we will be able to capture two spatiallyseparated images, one from the initial particle and one from the same cluster at a later stage of thephoto-induced transformation.
[1] C. Bostedt et al. PRL 108, 093401 (2012)[2] T. Gorkhover et al. PRL 108, 245005 (2012)

A6

Spectroscopy and dynamics

Momentum mapping of fragment ions generated upon Coulomb explosions ofdichloroethylene isomers in intense laser fields
Yoriko Wada,1 Hiroshi Akagi,2 Ryuji Itakura,2 Tomonari Wakabayashi,1 and Takayuki Kumada2
1
2

Department of Chemistry, Kindai University, Higashi-Osaka, Japan

Kansai Photon Science Institute, Japan Atomic Energy Agency, Kizugawa, Kyoto, Japan

Coulomb explosions are common features observed in the experiments of photon-moleculeinteractions using femtosecond laser pulses of high peak intensity. Extensive research activities
are found in literatures, concerning the understanding of fundamental processes of multi-photon
absorption, ionization forming multiply charged ions, and fragmentation followed by Coulomb
explosions. Despite the knowledge having been accumulated so far, it is rare to find an extensionof the Coulomb explosion process to analytical purposes in the molecular structure research. We
present our recent studies on the momentum mapping of fragment ions generated upon Coulomb
explosions of three isomers of dichroloethylene to discuss distinguishability of these isomers using
the mapping of kinetic characters of fragment ions in a momentum space.

Z-1,2-dichroloethylene

E-1,2-dichroloethylene

1,1-dichroloethylene

The three isomers, especially E-1,2-dichroloethylene, exhibited clearly different patterns in thecorrelation mapping of directions for the leaving cationic fragments, as already reported in theliterature [1]. Moreover, we analyzed the velocity as well as the direction for the fragment ion in a
momentum space to find that the momentum-mapping pattern is strongly influenced by thedifference in the intensity of laser fields. This is an indication for the next step for an application of
the Coulomb explosion to the molecular structure research for some molecular complexes [2-4].
References[1] T. Yatsuhashi, N. Nakashima, and J. Azuma, J. Phys. Chem. A 117 (2013) 1393.
[2] Y. Wada, T. Wakabayashi, and T. Kato, J. Phys. Chem. B 115 (2011) 8439.
[3] Y. Wada, Y. Morisawa, and T. Wakabayashi, Chem. Phys. Lett. 541 (2012) 54.
[4] Y. Wada, K. Koma, Y. Ohnishi, Y. Sasaki, and T. Wakabayashi, Eur. Phys. J. D 66 (2012) 322.

Spectroscopy and dynamics

A7

Vibrational Spectroscopy of Monolayer Protected Gold Clusters: A Close Lookat the Au-S Interface
Birte Varnholt,1 Patric Oulevey,1 Igor Dolamic,1 and Thomas Bürgi1
1

Department of Physical Chemistry, University of Geneva, Geneva, Switzerland

The nature of the thiolate - gold interface on flat surfaces as well as on nanoparticles is intensively
studied recently, mainly triggered by recent structure determination of some thiolate-protected
gold clusters, which challenges the standard model developed some time ago for self-assembled
monolayers of thiols on gold.[1] Vibrational spectroscopy is one way to discriminate bondstrengths and geometry sensitively. The low-wavenumber region, which contains the Au-S and
Au-S-C vibrations, can be investigated with far-infrared and Raman spectroscopy. With thesemeans we studied thiolate-protected gold clusters with surface structures known to be composedof monomeric (S-Au-S) and dimeric (S-Au-S-Au-S) binding units.[2,3]DFT calculations on the well-known Au38L24 cluster allow discriminating the spectral contributionsof such units. The assignment can be transferred to clusters with different surface composition. A
systematic shift of the Au-S-C bending allows estimating the number of monomeric and dimericunits.
Recently, a number of thiolate-protected gold clusters were reported that do not obey theelectronic shell closing magic numbers. It is assumed that the ligand structure plays a decisive role
for the formation of stable clusters. We will elucidate the spectra of a series of Au25L18 clusters withvarying aliphatic chain lengths and a number of sterically demanding ligands to obtain insight into
ligand-gold and ligand-ligand interactions on the clusters.
The metal-sulfur vibrations are furthermore sensitive to the metal type and therefore allow to shedlight on the position of the different metals of bimetallic alloy clusters. The catalytic activity of thelatter depends on the availability of the active metal to the substrate (core vs. staples) andvibrational spectroscopy is therefore a valuable tool for their characterization.

References[1] H. Häkkinen, Nat. Chem. 4 (2012) 443-455[2] I. Dolamic, B. Varnholt, T. Bürgi, Phys. Chem. Chem. Phys. 15 (2013) 19561-19565[3] B. Varnholt, P. Oulevey, S. Luber, C. Kumara, A. Dass, T. Bürgi J. Phys. Chem. C 118 (2014)
9604-9611

Spectroscopy and dynamics

A8

Vibrational spectroscopy of Au-nanocluster single crystals
Jaakko Koivisto,1 Kirsi Salorinne,1 Satu Mustalahti,1 Tanja Lahtinen,1Sami Malola,2 Hannu Häkkinen,1,2 and Mika Pettersson.1
1

Department of Chemistry and 2Department of Physics, University of Jyväskylä,
FI-40014, Jyväskylä, Finland.

We have measured the IR-spectra of [Au25(PET)18]-, 0, + and Au144(PET)60 -nanoclusters (PET =phenylethylthiolate, SC2H4Ph) in single crystals and solvated in deuterated DCM. In solvatedclusters the ligand vibrations are very weakly perturbed by the attachment to the gold cluster, but
in the crystals the vibrations are significantly broadened and the peak-shape changes fromLorentzian to Gaussian, indicating inhomogeneous broadening mechanism. For Au25(PET)18
crystals structural characteristics found in the X-ray crystal structure, such as the trans/gauche-isometry, is observed in the aliphatic C-H-stretching region, while in the Au144(PET)60 crystals
these peaks are quite featureless. For the negatively charged [Au25(PET)18]- -clusters thealkane-chains of the TOA+ (tetraoctylammonium) -counter-cation show significant disorder in the
crystal, which is also observed clearly in the IR-spectrum as strong broadening of the TOA+
aliphatic C-H -stretching (2800-3000 cm-1) and CH2-bending (1450 cm-1) modes. Similar
broadening seen in the IR-spectrum of crystalline Au144(PET)60 indicates that the ligands are foundin numerous different conformations in the crystal. The observed disorder of the ligand-layer in the
Au144(PET)60-crystals indicates that while the cluster cores form a periodic structure in the crystals,
the ligand layer between the cores does not. This may explain the difficulties in obtaining single
crystal X-ray -structure of the Au144(PET)60-cluster. The overtone and combination vibration
intensities compared to fundamentals are dramatically increased in the crystals, indicating
substantial coupling of the vibrational modes. The intensities of the overtone bands are stronger in
Au25-crystals than in Au144, indicating that the effect is caused by the crystal packing rather thanthe electronic, e.g. surface enhanced IR-absorption, properties of the Au-core.
[1] Koivisto; Salorinne; Mustalahti; Lahtinen; Malola; Häkkinen; Pettersson, J.Phys.Chem.Lett.,
2014, 5, p. 387-392.
[2] Zhu; Aikens; Hollander; Schatz; Jin, J.Am.Chem.Soc., 2008, 130, p. 5883-5885.
[3] Heaven; Dass; White; Holt; Murray, J.Am.Chem.Soc., 2008, 130, p. 3754-3755.

Spectroscopy and dynamics

A9

Two-color IR-UV spectroscopy of NbnCm clusters
Valeriy Chernyy,1 Joost Bakker,2 and Andrei Kirilyuk1
1
2

Radboud University Nijmegen, IMM, 6525 AJ Nijmegen, The Netherlands

Radboud University Nijmegen, FELIX facility, 6525 ED Nijmegen, The Netherlands

Infra-red (IR) vibration spectroscopy is a powerful and reliable method for probing vibrationalmodes, that provide a fingerprint of the cluster geometry [1]. There are several approaches to themeasurements of the vibrational spectra, such as IR Resonance Enhanced Multiphoton Ionisation(IR-REMPI) [2], IR Multi Photon Dissociation Spectroscopy [3], or two-color IR-UV ionization
spectroscopy [4]. The last technique is interesting not only because of universality, but also as amethod with an extra degree of freedom for the electronic states. Here we use IR-UV ionization
spectroscopy to study the excitation of vibrational modes and the resulting effect on the ionization
process in gas-phase NbnCm clusters. The advantage of this system is that IR-REMPI was shown
to work on some of the vibrational lines [5], which provides an excellent starting point.
The experimental approach we used is the following: a cluster is excited by an infrared light pulse(pump), produced by the Free Electron Laser for Infrared eXperiments (FELIX), transferring thecluster from the ground to a vibrationally excited state. After that the excited system can be ionisedwith the UV pulse with the photon energy that is not sufficient for a single-photon ionisation of the
non-excited cluster. In order to record vibrational spectra the experiments were done with fixed UV
wavelength as a function of the IR frequency. The ionization efficiency for the two-color IR+UV
process was normalized to the efficiency of the UV only process on a shot-to-shot basis.
The observed response types can be divided into three groups: (i) there is a high signal from direct
IR-REMPI mechanism, but no increase observed with the additional UV radiation, probably
because of the extremely high efficiency of IR-REMPI in these clusters; (ii) the clusters also
demonstrate some features on IR-REMPI type of spectra, but these features become stronger andbetter defined in IR-UV experiment; (iii) the most interesting is where there is no signal from
IR-REMPI but there are features in IR-UV type of spectra. The difference indicates the effective
temperature of the clusters. A complete set of vibrational spectra is thus obtained for NbnCm
clusters; the identification of the geometric conformations with the help of DFT is in progress.
Reference(s)[1] C. Ratsch et al., J. Chem. Phys. 122, 124302 (2005).
[2] G. von Helden et al., Phys. Rev. Lett. 79, 5234 (1997).
[3] W.J.C. Menezes and M.B. Knickelbein, J. Chem. Phys. 98, 1856 (1993).
[4] A. Fielicke et al., J. Chem. Phys. 131, 171105 (2012).
[5] D. van Heijnsbergen et al., Phys. Rev. Let. 89, 013401 (2002).

A10

Spectroscopy and dynamics

Comparative study of ultrafast relaxation dynamics of Au144(C2H4Ph)60 and
Au102(pMBA)44 nanoclusters by using mid-IR transient absorption spectroscopy
Satu Mustalahti1, Pasi Myllyperkiö1, Tanja Lahtinen1, Sami Malola2, Kirsi Salorinne1, Jaakko
Koivisto1, Hannu Häkkinen1,2 and Mika Pettersson1
1

Department of Chemistry, Nanoscience Center, P.O. Box 35, FI-40014 University of Jyväskylä,
Finland2

Department of Physics, Nanoscience Center, P.O. Box 35, FI-40014 University of Jyväskylä,
FinlandUltrafast electronic relaxation and vibrational cooling dynamics of Au144(C2H4Ph)60 and
Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) nanoclusters were studied by using
femtosecond transient mid-IR spectroscopy. In this study visible or NIR pump pulses were used toelectronically excite the sample and a mid-IR pulse was used to probe the system dynamics bymonitoring transient absorption of vibrational modes of the ligands. Solutions of highly
monodisperse samples were used for both clusters.
For Au144(C2H4Ph)60 visible pump pulse prepares an electronic state localized in the gold core.
The subsequent electronic relaxation via electron-phonon coupling was found to occur with time
constant of 1.5 ps followed by vibrational relaxation and heat dissipation into the solvent with 29 pstime constant. The excitation energy dependence of electronic relaxation time constant, which istypical for metallic clusters, was also observed for Au144 species thus conforming previous results[1]. For Au102(pMBA)44 cluster a drastically different type of relaxation dynamics similar to that ofmolecular systems is observed. Also formation of a long lived excited species (> 1 ns lifetime) isobserved, which indicates the existence of several pathways for electronic relaxation in Au102
species.
The obtained results establish an important correlation between exact cluster composition, andenergy relaxation and dissipation dynamics for studied systems. The results also clearly indicatethat molecular to metallic behavior transition occurs somewhere between these two cluster sizes
as has previously been suggested by studies of the onset for electronic absorbance for
Au102(pMBA)44 and Au144(C2H4Ph)60 [2, 3].
References[1] C. Yi, M. A. Tofanelli, C. J. Ackerson, and K. L. Knappenberger, Jr., J. Am. Chem. Soc. 135(2013) 18222[2] E. Hulkko, O. Lopez-Acevedo, J. Koivisto, Y. Levi-Kalisman, R. D. Kornberg, M. Pettersson,and H. Häkkinen J. Am. Chem. Soc. 133 (2011) 3752.
[3] J. Koivisto, S. Malola, C. Kumara, A. Dass, H. Häkkinen, and M. Pettersson J. Phys. Rev. Lett.
3 (2012) 3076.

Spectroscopy and dynamics

A11

Characterization of counter ions in solutions using thiol molecules adsorbed on
silver nanoparticles
Saori Handa, Yingying Yu, Masayuki Futamata
Graduate School of Science and Engineering, Saitama University, Saitama, JapanTo exploit a gap mode plasmon in surface enhanced Raman scattering (SERS) most efficiently,
we formed flocculates of Ag nanoparticles (AgNPs)1,2) using electrostatic interaction between
dissociated p-mercaptobenzoic acid (PMBA), protonated p-aminothiophenol (PATP) and theircounter ions, as well as van der Waals force between neutral PMBA, PATP and AgNPs. Adsorbed
state of PMBA and PATP in addition to trapped counter ions was elucidated using enormous
SERS enhancement in a flocculation method. Indeed, we found that AgNPs coated with
PATP-SAM feasibly formed flocculates under uncontrolled pH conditions. Because pH in PATP
aqueous solutions (10-4 M) is close to neutral, 8.4, larger than pKa of 6.1 for the ammonium group(-NH3+) in PATP, neutral species containing –NH2 are predominant. Accordingly, van der Waals
attractive potential much larger than thermal energy between AgNPs adsorbed by neutral
PATP-SAM film works for flocculation. In contrast, AgNPs coated with PATP-SAM were isolated at
pH=3-4, much lower than pKa for –NH3+ in PATP, owing to electrostatic repulsion between AgNPs
with protonated amino groups. This was supported by flocculation of AgNPs after the addition of
Na2SO4 (5 mM) or HClO4 (5 mM), whereas isolated AgNPs were sustained at slightly higher pHwith restricted ionic strength such as pH=4-5 in 10-4 M HClO4 solutions. These distinct features
depending on ionic strength are explained by DLVO theory for colloidal particles. In contrast,
flocculates of AgNP-PATP+…Xn-…+PTAP-AgNP (here Xn- =SO42- or ClO4-) provided pronounced
SERS spectra of trapped anions such as symmetric stretching mode S(SO42-) peak at 975 cm-1
and S(ClO4-) peak at 931 cm-1 at pH<3 with sufficiently high ionic strength, in addition to thosefrom PATP at 1594, 1490, 1180, 1075, 801, 630, and 389 cm-1. Thus, target anions in solution
were successfully trapped and characterized using electrostatic interaction with ammonium
cations of PATP-SAM on AgNPs. SERS spectra observed for protonated PATP+ are essentiallythe same as observed for PATP in literature3,4). Electrostatic interaction between PATP+ (-NH3+)and SO42- and ClO4- ions was also supported by Raman spectral changes for protonated andneutral PATP molecules. Interestingly, SERS spectrum of neutral PATP observed in flocculates of
AgNPs is different from that in literature3,4), which consists of Raman bands observed here inacidic conditions at 1597, 1490, 1174, 1074, 972, 802, 628, and 390 cm-1 attributed to PATP+(-NH3+), and those of so-called ‘dimer bands’ at 1420, 1378 and 1139 cm-1 in neutral pH. TheseSERS spectra in literature are observed for PATP molecule on Ag or Au nanostructures adsorbed
from ethanol solutions3,4). Our SERS spectra from neutral PATP, adsorbed in acidic conditions
followed by the addition of NaOH solution to be pH8, did not change with duration of laser
irradiation at >10W/m2, indicating photochemical dimerization of PATP was suppressed.
Probably, this is benefited by immediate flocculation of AgNPs with neutral PATP, of which
re-orientation is restricted to cause photochemical reactions at a nanogap. Also huge SERS
enhancement (G) of 109-1010 observed at a nanogap in flocculates of AgNPs assures negligible
contribution from plausible dimers at marginal sites, outside the nanogap, with G104 on AgNPs,
where PATP-SAM may cause photochemical reactions with PATP molecules in solutions.
Experimental results using PMBA-SAM films on AgNPs will also be presented at the conference.
References: [1] M. Futamata et al., J. Phys. Chem. C 114, 7502, 2010. [2] Y. Yu et al., Chem.
Phys. Lett. 560, 49, 2013. [3] Y. Huang et al., J. Am. Chem. Soc. 132, 9244, 2010. [4] X. Tian et al.,RSC Adv. 2, 8289, 2012.

Spectroscopy and dynamics

A12

Highly-sensitive gap mode Raman spectroscopy on various substrates
Maho Ishikura, Hiroki Suzuki, Masayuki Futamata*Graduate School of Science and Engineering, Saitama University, Saitama, JapanTo elucidate extremely small amount of adsorbates, a gap mode in surface enhanced Raman
scattering (SERS)1-3) was applied to various substrates including metals and dielectric materials.
We obtained sufficiently large 106-107 enhancement factor for Raman scattering signals fromthiophenol (TP) adsorbed on various substrates such as Au, Pb, Sn, V, Cu, Ni, Zn, Al, Pt, stainlesssteel, and even on Si by immobilization of gold nanoparticles (AuNPs with a radius of 15 nm).
Furthermore, we found that these enhancement factors are not affected by optical properties ofsubstrates but inherently determined by dielectric properties and sizes of AuNPs. Finite differencetime domain (FDTD) calculations anticipate enormous enhancement in electric field at a nanogap
between metal nanoparticles and metal substrates at appropriate excitation wavelengths. Indeed,108-1010 of Raman enhancement is experimentally obtained for various thiol monolayers on silver
substrates after the immobilization of silver nanoparticles (AgNPs)4,5). Here, AuNPs were utilized
to investigate more details on a gap mode Raman spectroscopy to establish this as an analytical
tool. FDTD calculations yielded that: (1) the resonance wavelength for a gap mode is primarily
determined by AuNP, i.e. its optical constants and size, which is 560 nm for a spherical AuNP witha radius (rAuNP) of 15 nm on various metal substrates used here. (2) Not only metal substrates but
also dielectrics with large optical constants (sub) compared to that of surrounding media (med),such as Si with an optical constants larger than 10 (sub) at 632 nm in air (med=1), provides
pronounced enhancement (106-107) in SERS. This prediction is simply explained by the following
equation: psub’ = p  (sub - med) / (sub + med), where mirror image dipole in substrate (psub’) is
induced by an electrical dipole in AuNP (p). (3) Larger AuNP provides larger enhancement inelectric field at a nanogap, for instance enhancement in the electric field from 5.6103 (at rAuNP=15nm) to 4104 - 9104 (at rAuNP=50 nm) on various metal substrates, yielding 109-1010 of SERS
enhancement. Larger AuNP broadens the width of resonance wavelength, for instance from 80 nm(rAuNP=15 nm) to 190 nm (rAuNP=50 nm), due to increased contribution of multipoles. Thisobservation facilitates wider application of a gap mode in SERS, in which various laser
wavelengths are available. Next, we experimentally investigated a gap mode between AuNPs andvarious substrates, such as Au, Pb, Sn, V, Cu, Ni, Zn, Al, Pt, stainless steel, and Si (>10) and
BK-7 (2.1) cover slip, to ensure anticipated enhancement in SERS. We found that: (1)immobilization of AuNPs (rAuNP=15 nm) provided pronounced enhancement factors of 106-107 for
TP at a nanogap. (2) Even silicon wafer substrates provided enhancement of 106 in SERS by theimmobilization of AuNPs. (3) Larger enhancement in Raman scattering signal was confirmed forlarger AuNPs, for instance larger enhancement by a factor of 10 was observed for Zn and Si
substrates for AuNPs with a radius (r) of 50 nm compared to that with r=15 nm. Detailed analysis
on the size effect using much larger AuNPs will also be presented. Thus, we confirmed that a gap
mode is relevant not only for various metals with large damping, but also for dielectric materials
with large optical constants, and larger enhancement factor for larger AuNPs. These observations
probably facilitate wider application of highly-sensitive gap mode Raman spectroscopy.
References: [1] P. K. Aravind et al., Surf. Sci. 124, 506, 1984. [2] K. Ikeda et al., J. Phys. Chem.
116, 20806, 2012. [3] K. Kim et al., J. Phys. Chem. C 115, 21047, 2012. [4] H. Suzuki et al.,Vibrational Spectrosc. 72, 105, 2014. [5] H. Chiba et al., Vibrational Spectrosc. 73, 19, 2014.

Spectroscopy and dynamics

A13

In-situ produced BiOx nanoparticles: Studied in a beam and as deposited byphotoelectron spectroscopy
Mikko-Heikki Mikkelä,1 Maxim Tchaplyguine,1 Chaofan Zhang2, Tomas Andersson2, Erik Mårsell3
and Olle Björneholm2
1
2

MAX IV Laboratory, Lund University, Lund, Sweden

Department of Physics and Astronomy, Uppsala University, Uppsala, Sweden
3

Department of Physics, Lund University, Lund, Sweden

Study of bismuth oxide (BiOx) nanoparticles has attracted interest due to their relevance forcatalytic and medical applications [1,2]. In the present work we have investigated BiOx
nanoparticles in a particle beam – unsupported – and as deposited on Si(111) substrate, using
X-ray photoelectron spectroscopy (XPS). The experiments were carried out in MAX IV laboratory,
Sweden, at the soft X-ray beamline I411 (hv = 40 – 1500 eV). Studied nanoparticles were formed
using reactive sputtering based gas-aggregation source [3] and XPS investigation of unsupported
particles in a beam and deposition was carried out in-situ in the same experimental chamber andthus effects of deposition and changes in the properties of unsupported nanoparticles could be
investigated.
XPS results suggest that depending on the settings of the reactive sputtering, metallic Bi,
combined Bi-BiOx or pure BiOx nanoparticles are produced and that relative Bi-BiOx ratio remains
somewhat unchanged upon the deposition. In the previous studies of PbOx nanoparticles using
the same experimental setup [4], a heterogeneous oxide-core and metallic-shell structure wassuggested and similar dual component composition is also expected for Bi-BiOx particles of thiswork. XPS of deposited particles has been also used to investigate how the oxidation state of thedeposited particles might change relative to the unsupported species. In addition to XPS we havealso utilized scanning electron microscopy (SEM) to investigate the nanostructures formed by thedeposited particles and to obtain information about the particle size.
Reference(s)[1] L. Zhang, W. Wang, J. Yang, Z. Chen, W. Zhang, L. Zhou, S. Liu, Appl. Catal. A 308 (2006)
105.
[2] K. Bogusz, M. Tehei, C. Stewart, M. McDonald, D. Cardillo, M. Lerch, S. Corde, A. Rosenfeld,
H.K. Liua, and K. Konstantinov, RSC Adv. 4 (2014) 24412.
[3] M. Tchaplyguine, S. Peredkov, H. Svensson, J. Schulz, G. Öhrwall, M. Lundwall, T. Rander, A.
Lindblad, H. Bergersen, S. Svensson, M. Gisselbrecht, S. Sorensen, L. Gridneva, N.
Mårtensson, and O. Björneholm, Rev. Sci. Instrum 77 (2006) 033106.
[4] C. Zhang, T. Andersson, S. Svensson, O. Björneholm, and M. Tchaplyguine, Phys. Rev. B 87
(2013) 035402.

A14

Spectroscopy and dynamics

Photofragment-ion imaging from mass-selected cluster ionsusing a linear-type tandem reflectron
Kenichi Okutsu, Kenichiro Yamazaki, Keijiro Ohshimo, and Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki,
Aoba-ku, Sendai 980-8578, Japan
We have been studying photodissociation dynamics of mass-selected cluster ions by using areflectron time-of-flight mass spectrometer combined with an ion-imaging detector. In the present
study, we have developed an apparatus of a linear-type tandem reflectron, in place of anangular-type reflectron which was used in our previous study [1]. Using this apparatus we areultimately aiming to obtain highly-resolved photofragment-ion images which satisfy velocity map
imaging conditions. After construction of the apparatus, the performance has been checked by theultraviolet photodissociation experiment of an Mg+-Ar complex ion.
Fig. 1 shows a schematic diagram of theapparatus. Magnesium-argon binary cluster ions
including

Mg+-Arwere

produced

by

laser

vaporization, and they were mass-selected by thetime-of-flight mass spectrometer. The Mg+-Ar ion
was then reflected with the "1st reflectron".
Because no pulsed voltage was applied on the"2nd reflectron" at this moment, the ions pass

Fig. 1 Schematic diagram of the apparatus

through these electrodes without changing theirvelocities. After the first reflection, the ions were irradiated with linearly polarized dissociation laser(fourth harmonic of a Nd:YAG laser, 266 nm) at the middle of the two reflectrons. Photofragment
Mg+ ions were then reflected with the 2nd reflectron, and detected as ion images by micro channel
plate with phosphor screen. Finally the optical image signals were accumulated using a CCD
camera.
Electronic transition applied in this experiment has alocalized nature of 3pz ← 3s excitation on Mg+, andthus the transition dipole moment is parallel to the
Mg-Ar bond axis [2]. The Mg+ fragment image wasobserved as shown in Fig. 2, by changing thepolarization direction of the dissociation laser (E)with respect to the ion beam direction (Z). The split
ion image of Mg+ parallel to E was observed at E⊥Z
condition, as expected.

Fig. 2 Observed images of fragment ion
Mg+ for E // Z (left), E⊥Z (right)

References[1] H. Hoshino, Y.Yamakita, Y.Suzuki, M.Saito, K.Koyasu, and F. Misaizu, 16th ISSPIC, B25 (2012).
[2] J. S. Pilgrim, C. S. Yeh, K. R. Berry, and M. A. Duncan, J. Chem. Phys. 100 (1994) 7945.

Spectroscopy and dynamics

A15

Time Resolved Study of EUV-FEL Triggered Nano-Plasma of Rare-Gas Clusters
K. Nagaya1,2, T. Sakai1, T. Nishiyama1, K. Matsunami1, S. Yase1, M. Yao1, H. Fukuzawa2,3,
K. Motomura3, T. Tachibana3, S. Mondal3, K. Ueda2,3, S. Wada2,4, H. Hayashita4, N. Saito2,5,
T. Togashi2,6, M. Nagasono2, M. Yabashi2
123Department of Physics, Kyoto University, Kyoto 606-8502, JapanRIKEN SPring-8 Center, Kouto 1-1-1, Sayo, Hyogo 679-5148, Japan

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai
980-8577, Japan

4

Department of Physical Science, Hiroshima University, Higashi-Hiroshima 739-8256, Japan
5
6

National Metrology Institute of Japan, AIST, Tsukuba 305-8568, Japan

Japan Synchrotron Radiation Research Institute, Hyogo 679-5198, JapanThe free electron laser (FEL) light sources based on self-amplified spontaneous-emission (SASE)
are opening new research fields of the interaction of matters with intense laser pulses in the shortwavelength region. Pioneering works for rare-gas clusters [1-3] revealed the importance ofnano-plasma formation for the FEL-matter interaction process. Here we discuss nano-plasma
dynamics using pump-probe scheme, which was proposed by the molecular dynamics simulations
study for small rare-gas clusters [4]. We carried out EUV-FEL pump – near infra-red (NIR) laser
probe experiments at the SPring-8 compact SASE source (SCSS) test facility [5].
We have carried out time-of-flight (TOF) measurements of fragment ions from xenon clusters(N~5,000) and neon clusters (N~5,000) as a function of delay time (t) between the EUV-FEL
pulse ( =51nm for xenon clusters and 61nm for neon clusters) and the NIR laser pulse (=800nm). We confirmed the emission of energetic highly charged xenon ions up to around Xe 15+
for xenon clusters from the analysis of TOF spectra, suggesting the enhanced heating of
nano-plasma due to surface plasma resonance. The signature of surface plasma resonance gives
an evidence for the nano-plasma formation from rare-gas clusters by intense EUV-FEL irradiation.
We found similar enhancement of highly charged ions for neon cluster, though the delay timedependence is different between xenon cluster and neon cluster, suggesting the difference of thenature of nano-plasma produced by EUV-FEL irradiation.
We are grateful to SCSS Test Accelerator Operation Group at RIKEN for continuous support in thecourse of the studies. This study was supported by the X-ray Free Electron Laser Utilization
Research Project and the X-ray Free Electron Laser Priority Strategy Program of Ministry of
Education, Culture, Sports, Science, and Technology of Japan (MEXT), by Grants-in-Aid (No.
23241033 and No. 23600006) from the Japan Society for the Promotion of Science (JSPS).
Reference(s)[1] C. Bostedt et al., New J. Phys. 12 (2010) 083004.
[2] B. Ziaja, H.Wabnitz, F.Wang, and E.Weckert, T. Moeller, Phys.Rev. Lett. 102, 205002 (2009).
[3] M. Arbeiter and Th. Fennel, Phys. Rev. A 82, 013201 (2010).
[4] C. Siedschlag and J. M. Lost, Phys. Rev. A 71, 031401(R) (2005).
[5] H. Shintake et al., Nature Photon. 2, 555 (2008).

A16

Spectroscopy and dynamics

X-ray absorption spectroscopy of size-selected cerium oxide clusters
Tetsuichiro Hayakawa,1 Masashi Arakawa,2 Shun Sarugaku,2 Kota Ando,2 Kenichiro Tobita,2Tomonori Ito,2 Kazuhiro Egashira,1 and Akira Terasaki2,3
1

East Tokyo Laboratory, Genesis Research Institute, Inc., Chiba, Japan2

3

Department of Chemistry, Kyushu University, Fukuoka, Japan

Cluster Research Laboratory, Toyota Technological Institute, Chiba, Japan

Bulk ceria (CemOn) exhibits oxygen storage/release behavior and is applied to catalysts or catalyst
supports. It is known that the charge state of Ce atoms and the oxygen storage behavior of ceria
are closely related to each other. We are investigating cerium oxide clusters as model systemsof active sites of ceria catalysts by using X-ray absorption spectroscopy (XAS).

XAS is a

powerful tool to investigate electronic (and geometric) properties of multi-element systems
because of its element specificity. In this study, local charge states of Ce and O atoms insize-selected free cerium oxide clusters are probed via spectral shifts in X-ray absorption.
Cerium oxide cluster ions are produced by a magnetron sputtering cluster ion source, transported
by ion-guides and ion-deflectors, size-selected by a quadrupole mass filter, and admitted into alinear quadrupole RF ion-trap. The linear ion trap accumulates size-selected cluster ions, which
are otherwise extremely dilute. The ions thus stored are irradiated with a soft X-ray beam from asynchrotron (BL-7A in Photon Factory, KEK, Japan), and are fragmented upon X-ray absorption.
An X-ray absorption spectrum is measured through the fragment-ion yield as a function of thephoton energy.
X-ray absorption of small cerium oxide clusters (CemOn+; m=2, 3) was measured in the energy
range of Ce M-edge (ca. 880 eV) and O K-edge (ca. 530 eV). CeO+, Ce+ and Ce2+ were
produced as dominant fragment ions, while background ion signal was negligibly weak. X-ray
absorption spectra in Ce M-edge region consisted of two prominent peaks corresponding to Ce
M5- and M4-“white lines”. The Ce M-edge spectra of Ce2O3+ and Ce2O5+ show higher peakenergies and smaller M5/M4 intensity ratio for Ce2O5+ than for Ce2O3+. These features indicatethat Ce atoms in Ce2O5+ are more positively charged than in Ce2O3+, which is consistent with thehigher oxygen content in the former. Systematic blue-shifts in the spectra were clearly observed
also for Ce3On+ with increase in n. In the presentation, charge states of Ce and O atoms will be
discussed in the context of geometric structures of the clusters.

Spectroscopy and dynamics

A17

Photodepletion spectroscopy of silver cluster cations
in a temperature-controlled ion trap
Tomonori Ito, Kenichiro Tobita, Masashi Arakawa, and Akira Terasaki
Department of Chemistry, Kyushu University, Fukuoka, Japan
Optical properties of metal vary dramatically with its size, e.g. metal nanoparticles exhibit broad
spectra caused by collective excitation of electrons, whereas atoms show spectral lines resulting
from transitions between atomic orbitals. Metal clusters provide an opportunity to investigate
emergence of a collective behavior of electrons in the intermediate size range. Electronic
structures should be reflected in a spectral profile of absorption, which depends on the cluster size
and temperature. In this work, we report photodissociation action spectra of silver cluster cations
with a focus on size and temperature dependence for a systematic study of electronic transitions
in metal clusters.
Silver cluster cations, Agn+ (n = 8–14), were produced with a magnetron sputtering ion source andmass-selected by a quadrupole mass filter. They were stored in a linear radio-frequency ion trap
and irradiated with an UV laser tunable between 285 and 335 nm. Dissociation yields were
evaluated as decrease in the parent ions by laser irradiation, i.e., the “photodepletion” method was
employed.
Figure 1 shows photodissociation action spectra of Ag9+ measured at 300 and at ~110 K. The
spectrum at 300 K shows four broad peaks with full widths at half maximum (FWHM) of about ~0.1
eV. When the ion trap and the buffer gas were cooled down to ~110 K, the peaks became
narrower and some of them were blue-shifted. The observed spectral profiles show that the opticalabsorption originates not from collective electronic excitation but rather from single-electrontransitions between molecular orbitals, as evaluated by widths and integrated intensities ofabsorption. The spectral sharpening at a lower temperature is attributable to lowering thevibrational quantum number in the initial ground electronic state, which reduces hot-band
contributions. Temperature-dependent spectra with similar integrated absorption intensities wereobserved as well for Agn+ (n = 8–14). These results imply that molecular nature of electronic
structures is retained at least up to n = 14.

Figure 1. Photodepletion spectra of Ag9+ measured atroom temperature (closed circles) and ~110 K (open squares).

Electronic structure and quantum effects

A18

Geometry, Electronic, and Magnetic properties as well as selective O 2 and CO
adsorption on AunRhm clusters
Marcela .R. Beltrán1, Fernando. Buendía1
1

Universidad Nacional Autónoma de México, Instituto de Investigaciones en Materiales, Apdo.
Postal 70-360, C.P. 04510, Del. Coyoacán, México D.F. México

The chemical reactivity of gas-phase transition metal clusters toward various molecules has been
the subject of numerous investigations, motivated by the intrinsic interest in clusters as novel
nanoscale catalysts, as well as by the lessons that may be learnt from such studies pertaining tocatalysis by supported metal clusters and the adsorption and reactivity mechanisms of extended
metal surfaces. Recently there has been a growing interest in the chemical properties of gold nanoclusters and their potential use as nanocatalysts. In early experiments a definite pattern of oxygen
adsorption to negatively charged small gold clusters has been detected, where only anionicclusters with an even number of atoms (odd number of valence electrons) showed significant O2
uptake1, whereas odd-numbered clusters either did not exhibit any propensity for reaction withoxygen1 or showed very weak reactivity. Also gold cluster anions that show a propensity foroxygen adsorption can also coadsorb carbon monoxide, thus suggesting them as possible model
catalysts for the CO oxidation reaction2,3. Base on those studies A systematic study of the stabilityof gold rhodium clusters, their electronic and magnetic properties as well as their behavior underoxygen rich and CO rich simulated atmospheres is presented. This study has been done using
density functional theory calculations. Their Infra red spectra, their binding energies, as well as
their vertical and adiabatic detachment energies are presented and discussed. On the other handtheir dissociation energies for different evaporation channels have also been calculated. The
influence of adsorbant atom(s) on the surface structure and the stability of the clusters is also
discussed.
References[1] Bokwon Yoon, Hannu Hakkinen, and Uzi Landman, J. Phys. Chem. A, 4066, 107 2003
[2] Ajay M. Joshi, W. Nicholas Delgas and Kendall T. Thomson, J. Phys. Chem. B. 23373, 110,
2006
[3] Mitsutaka Okumura, Yasutaka Kitagawa, Masatake Haruta, Kizashi Yamaguchi,
Applied Catalisis A: General, 37, 291, 2005

Electronic structure and quantum effects

A19

AB INITIO STUDY OF CATIONIC, ANIONIC AND
NEUTRAL AunRhm CLUSTERS
Fernando Buendía1 and Marcela R. Beltrán1
1

Universidad Nacional Autónoma de México, Instituto de Investigaciones en Materiales, C.P.
04510, México D.F. México

The determination of the geometric structure of transition metal clusters is a vital step towards
understanding cluster properties. Therefore any effort in this direction is essential for the future
possible applications and to the development of new technologies. Bimetallic clusters have drawn
considerable attention in recent years due to its capacity to enhance their electronic and catalytic
properties. In particular, transition metal doped gold clusters have been extensively investigatedboth, experimentally as well as theoretically [1,2]. These systems are interesting as doping withtransition metal atoms strongly changes the properties of the host cluster. The geometricstructures, relative stabilities, magnetic moments, and vibrational spectra of small cationic, anionicand neutral AunRhm clusters have been systematically studied through density functional theory(DFT) [3]. Our results show that the transition metal doping of gold clusters play a special roll in
their stabilities and their chemical activity.
References[1] W. Bouwen, F. Vanhoutte, F. Despa, S. Bouckaert, S. Neukermans, L. T. Kauhn, H. Weidele,P. Lievens, R. E. Silverans, Chem. Phys. Lett. 314, 227 (1999)[2] M. Heinebrodt, N. Mailinowski, F. Tast, W. Branz, I. M. L. Billas, T. P. Martin, J. Chem. Phys.
110, 9915 (1999)[3] R. Ahlrichs; M. Bär; M. Häser; H. Horn; C. Kölmel, Chem. Phys. Lett.162, 165 (1989)

Electronic structure and quantum effects

A20

Electronic and optical properties of hetero-assembled endohedral superatomic
clusters
Takeshi Iwasa1,2 and Atsushi Nakajima1,2
1

Nakajima Designer Nanocluster Assembly project, JST-ERATO, Japan2

Department of Chemistry, Keio University, Yokohama, Japan

Multielement gas-phase clusters including endohedrally doped silicon or aluminum magic clusters
show intriguing physicochemical properties such as electronic, magnetic, and optical properties.
Since these properties are dependent on the cluster size and compositions, the use of designer
endohedral clusters as potential building blocks for novel optoelectronic devices is attractive
challenging issue. For example, endohedral silicon and aluminum clusters such as Si 16M (M=Sc,
Ti, V) and Al12X (X=B, Si, P) are known to possess highly symmetric structures and atom-likeelectronic shells. When M=Ti and X=Si, these clusters show the closed electronic shell, like noble
gas atoms. Replacements of the endohedral atoms to those in the neighboring groups such as Sc
or V for Si16Ti and B or P for Al12Si give hole or electron, respectively, in the electronic shell,
invoking the p- or n-type semiconductor.
We have previously demonstrated that the Si16M clusters are possible building blocks to fabricate
cluster-based p-n or p-i-n junctions through the density functional theory study on thehetero-assembly of Si16M clusters [1]. In the present study, the electronic and optical properties ofhetero-assembly of Al12X are studied and the results are compared to those of Si16M. Furthermore,
the electronic structures are analyzed by projecting the Kohn-Sham orbitals of the monomer units
into the spherical harmonics to classify them from a superatom perspective [2].
The HOMOs and LUMOs of a hetero-assembly of Al12B-Al12P dimer are fairly localized to Al12B
and Al12P units, respectively, and can be labeled as FG and DG hybridized states. The
hetero-dimer has substantial charge carriers, which are estimated as the difference in electron
counts from the closed-shell Al12Si, with slight charge depletion in contrast to the case of Si16M.
The charge depletion occurs due to the electron delocalization, because the frontier orbitals of
Al12X consist mainly of surface Al atoms, whereas the frontier orbitals of Si 16M localize toendohedral M atoms. Analyses on the UV-Vis spectrum of the hetero-dimer, simulated bytime-dependent DFT calculations, show that the charge-transfer excited states would occur from
Al12B to Al12P in energy range up to 4 eV. These results suggest the potential applications of theseclusters to fabricate p-n junction for photovoltaic cells. When one or two Al12Si, which cancorrespond to an insulating semiconductor, is inserted between the hetero dimer, it is found toenhance the dipole moment of the hetero-assembled clusters.
References[1] T. Iwasa and A. Nakajima, J. Phys. Chem. C 116 (2012) 14071-14077.
[2] T. Iwasa and A. Nakajima, J. Phys. Chem. C 117 (2013) 21551-21557.

Electronic structure and quantum effects

A21

Electronic structure of rare-earth clusters: from number of 4f-electrons tomagnetism
Lars Peters1, Saurabh Ghosh2, Igor di Marco2, Biplab Sanyal2, Anna Delin2, Misha Litcarev2, Theo
Rasing1, Andrei Kirilyuk1, Olle Eriksson2, and Mikhail Katsnelson1
1

Radboud University Nijmegen, Institute for Molecules and Materials, Nijmegen, The Netherlands
2

Department of Physics and Astronomy, Uppsala University, Uppsala, Sweden

The majority of rare-earth atoms (with the exception of La, Ce, Gd and Lu) are divalent, while mostof the rare-earth bulk systems (except α-phase Ce, Eu and Yb) are trivalent [1]. In other words, anatom is described by the 4fn+16s2 configuration and the bulk by the 4fn[spd]3 one. Thus, by goingfrom the atomic limit to the bulk limit one 4f-electron is transferred to the [spd]-band. What
happens in the regime between these two limits, the cluster regime, is completely unknown. Will
the cluster be divalent, trivalent or perhaps mixed-valent? The resulting electronic structure plays
a major role in the resulting cluster properties, such as magnetism, polarizability or conductivity.
We address this fundamental question by using density functional theory (DFT) calculations. ThisDFT in its conventional form (LDA or GGA) is derived in the limit of a (nearly) uniform electron gas
and is therefore only suitable for weakly correlated delocalized electron systems. However, we are
dealing with the opposite case, that of strongly correlated localized electron systems. Therefore,
DFT is used to describe the delocalized [spd]-electrons in the cluster only and for the 4f-electronsa special approach is used. This approach is known as the Born-Haber cycle [2] and allows us toaccurately examine the required energy differences between a divalent, trivalent and mixed-valentcluster. This is done by first evaluating the energy differences in DFT between 4fn[spd]3, 4fn+1[spd]2
and 4fn+x[spd]3-x configurations in which intra and inter 4f-couplings are completely excluded.
Second, this exclusion is corrected for by using experimental data on the isolated rare-earth atom,which is justified since the 4f-shell in the atom, cluster or bulk is essentially the same.
As a result we derive that for example all Tb clusters are pure trivalent, while Sm and Tm clusters
show an abrupt change from pure divalent to pure trivalent at respectively a size of 8 and 6. In
contrast to expectations, no mixed-valence state was observed in the transition region.
With the electronic structure established we may proceed to understand the magnetic interactions
and resulting configuration of the rare-earth clusters. For example for Sm it follows directly from
Hund’s rules that a divalent cluster is non-magnetic (J=0), while a trivalent cluster is magnetic(J=2.5). In other words, the magnetism should only appear in clusters of 8 atoms and larger. Also
we show for Tb-clusters that the exchange coupling can be understood in terms of a competition
between double-exchange and super-exchange.
[1] Jensen, J. and Mackintosh, A.R. Rare Earth Magnetism (Clarendon Press, Oxford, 1991)[2] Delin, A., Fast, L., Johansson, B., Wills, J. M. and Eriksson, O. Method for calculating
valence stability in lanthanide systems. Phys. Rev. Lett. 79, 4637-4640 (1997)

Electronic structure and quantum effects

A22

Coexistence of Insulating and Metallic States, and other Unusual Electronic andMagnetic Properties of Pure and Doped Zinc Clusters
Andrés Aguado,1 Andrés Vega,1 Alexandre Lebon,2 and Bernd von Issendorff3
1

Department of Theoretical, Atomic and Optical Physics, Valladolid University, Spain
2

Laboratoire de Magnétisme de Bretagne, Brest University, France
3

Physikalisches Institut, Universität Freiburg, Germany

How many of the several attributes of the bulk metallic state persist in a nanoparticle containing afinite number of atoms of a metallic element? Do all those attributes emerge suddenly at a welldefined cluster size or do they rather evolve at different rates and in a broad size range? In thisposter, we address these fundamental questions through a conjoint experimental/theoreticalinvestigation of zinc clusters with up to 73 atoms. We show that the evolution of metallic properties
with size is not monotonous and rather displays reentrant insulating behavior at several sizes
following an electronic shell closing. Additionally, we report the observation of novel coexistence
phenomena involving different electronic phases: for some sizes, metallic and insulating electronic
states coexist within a single, Janus-like, nanoparticle; for the rest of sizes, we report thecoexistence of two weakly interacting metallic phases with different dimensionalities, localized
respectively at the shell and the core of the nanoparticle. This is due to an anomalously longcore-shell separation, which equips the shell and coreregions with largely independent structural,
vibrational and thermal properties, only weakly correlated to each other.
In a second part of the poster, we demonstrate that the cluster Zn17 doped with an endohedral Cr
impurity can be qualified as a magnetic superalkali cluster. We explain the origin of its high stability,
its low vertical ionization potential and its high total spin magnetic moment which amounts to 6μB,
exactly the value of the isolated Cr atom. With the aim of exploring the possibility of designing abistable magnetic nanoparticle, with a corresponding inter-unit exchange coupling, we also
consider the assembling of two such units through different contact regions and in different
magnetic configurations. Furthermore, we analyze up to which extent is the Zn shell able topreserve the electronic properties of the embedded Cr atom, both against coalescence of the two
superatoms forming the magnetically bistable nanoparticle, and upon the adsorption of an O2
molecule or even under an over-saturated oxygen atmosphere. Our results are discussed not only
emphasizing the fundamental physical and chemical aspects, but also with an eye on the newprospects that those Cr@Zn17 magnetic superalkali clusters (and others of similar kind) may
open in spintronics-, molecular electronics- or biomedical-applications.

A23

Electronic structure and quantum effects

Probing of an Adsorbate-Specific Excited State on an Organic
Insulating Surface by Two-Photon Photoemission Spectroscopy
Masahiro Shibuta,1 Naoyuki Hirata,1,2 Toyoaki Eguchi,1,2 and Atsushi Nakajima1,2
1

Department of Chemistry, Faculty of Science and Technology, Keio University, Japan
2

JST, ERATO, Nakajima Designer Nanocluster Assembly Project, Japan

Controlled assembly of functionalized nanoclusters or molecules is one of the promising
candidates to create novel nanomaterials. Although electrically conductive material, metals andsemiconductors, are often used as substrates, physical properties of adsorbed nanoclusters ormolecules are largely disturbed due to the strong interaction between adsorbates and substrates.
In this study, photo-excited electronic states of a ferrocene (Fc) molecule adsorbed on
decanethiolate self-assembled monolayer (SAM) formed on Au(111) substrate, which is known to
be chemically inert and electrically insulating [1], have been investigated by using two-photon
photoemission spectroscopy (2PPE). We have found that, on the SAM surface, Fc interacts withthe substrate very weakly and newly forms the excited states specific to isolated molecules
adsorbed on an insulating substrate [2].
A top of Figure 1 shows photon energy dependence of 2PPE

0.3 ML Fc /SAM

spectra for 0.3 monolayer (ML) of Fc on SAM plotted against an
p-pol.

intermediate energy relative to Fermi level (EF). By Fc adsorption, apeak labeled A* appeared at EF + 2.6 eV. The intensity of A* was

4.71

enhanced at the photon energy of 4.5 – 4.6 eV, indicating thatoccupied molecular orbital (HOMO) located at EF – 1.9 eV. The
polarization dependence of 2PPE spectra (Fig. 1 bottom) indicatesthat the electrons in A* are bound perpendicular to the surface

4.65

A

4.59

2PPE intensity

electrons in A* are resonantly excited from Fc-derived the highest

4.54
4.48

4.43
4.38
4.33
4.28

because it is only probed by p-polarized photon. It has been reported

4.23

that, for a free Fc molecule in gas phase, the first molecular Rydberg

A

state is formed at 5.1 eV above HOMO, which is about 0.5 eV higher

p-pol.

than resonance photon energy of A* (4.5 – 4.6 eV). From theses-pol.

experimental findings, it has been concluded that the A* is an excitedstate bound not only to the excited hole formed at the adsorbed Fc

hv
(eV)
4.77

4.54

2.0

2.5

3.0

Intermediate energy (eV)but also to the positive image charge induced in the substrate. The
A* is therefore specific to the isolated adsorbate on electricallyFigure 1. Photon energy

insulating substrate. Such an adsorbate-specific excited state, which(hv)

is not formed in a free molecule, will be responsible for uniquedependent 2PPE spectraof 0.3 ML Fc on SAM.

properties characteristic of adsorbates on the surface.

andpolarization

Reference[1] M. Shibuta, N. Hirata, R. Matsui, T. Eguchi, A. Nakajima, J. Phys. Chem. Lett. 3 (2012) 981.
[2] M. Shibuta, N. Hirata, T. Eguchi, A. Nakajima, J. Am. Chem. Soc. 136 (2014) 1825.

Electronic structure and quantum effects

A24

Full relativistic calculations of electronic and magnetic properties of small
cationic and neutral bismuth clusters
Josef Anton1, and Timo Jacob1, and Arne Rosen2
1

Department of Electrochemistry, University of Ulm, Ulm, Germany

2

Department of Physics, University of Gothenburg,Gothenburg, SwedenGroup-V elements show huge variability in their electrical, mechanical, and thermal properties –ranging from gaseous nitrogen to solid and brittle bismuth. Within the group-V elements, bismuth
is the only metal while arsenic and antimony are classed as semi-metals [1]. Under ambientconditions the most stable crystalline form of both bismuth and its lighter group V congeners is arhombohedral layered structure (α-As, α-Sb, α-Bi) with each atom surrounded by three nearest
neighbors within the layer and three atoms at a larger distance in the adjacent layers. In α-Bi,
these intra- and inter-layer distances differ by only 15% approaching the simple cubic structurewith a coordination number of six. Furthermore, unlike P4 (white phosphorous) and As4 (yellow
arsenic) a solid Bi4 form is unknown [1].
Relativistic effects such as the stabilization of the np1/2-orbital, destabilization of the np3/2-orbitaland spin-orbit coupling lead to a drastic changes in electronic and magnetic properties of a single
atom from Phosphor to Element 115 in group V [2]. For instance, in lighter elements of this group,
P, As, and Sb, their outermost p-levels are splitted by less than 0.6 eV and the p-electrons arecoupled according to the well-known LS-coupling scheme while in the heavy Element 115 theSpin-Orbit (SO) splitting of the outermost p-levels is about 4.7 eV and the p-electrons are coupledaccording to the jj-coupling scheme. Relativistic effects in Bi-atom where the fine splitting of the
p-levels is about 1.8 eV are very pronounced and lead to a break down the LS-coupling scheme
but they are still not strong enough to couple the p-electrons according to jj-coupling scheme.
These differences in the electronic structures of the atoms in the group V cause also thedifferences in the properties of their molecules and atomic clusters [2]. Thus, a proper theoreticaldescription of electronic and magnetic properties of e.g. Bi-clusters requires a self-consistenttreatment of all relativistic effects in the clusters.
In this contribution we will present our full relativistic 4-componet calculations on electronic andmagnetic properties of small cationic and neutral Bi-clusters which were performed with our full
relativistic DFT-code [3]. We also will compare our results with the recently published experimental
results [4].
References[1] N. N. Greenwood and A. Earnshaw, Chemistry of the Elements, 2nd Ed., Elsevier, 1997[2] V. Pershina, A. Borschevsky, J. Anton, and T. Jacob, J. Chem. Phys. 132, 194314 (2010).
[3] J. Anton, B. Fricke, E. Engel, Phys. Rev. A, 69, 012505 (2004).
[4] R. Kelting et al., J. Chem. Phys. 136, 154309 (2012).

Electronic structure and quantum effects

A25

Phase Transition Behavior and Ionic Conductivity of
Small Silver Iodide Quantum Dots
Takayuki Yamamoto,1 Hirokazu Kobayashi,1,2 Yoshiki Kubota,3 and Hiroshi Kitagawa1,2
1

Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto, Japan
2

Core Research for Evolutional Science and Technology (CREST),Japan Science and Technology Agency (JST), Tokyo, Japan3

Department of Physical Science, Graduate School of Science,
Osaka Prefecture University, Osaka, Japan

Much effort has been made to realize all-solid-state batteries. Silver iodide has been extensively
studied as one of the candidates for ionic conductors in solid electrolytes because thehigh-temperature α-phase shows superionic conductivity due to a sublattice melting of silver ions.
Below 147 °C, bulk silver iodide undergoes a structural phase transition from the α-phase into thepoorly-conducting /-phase, thereby limiting its application. On the other hand, nanoparticles
show different phase behavior from bulk due to nano-size effect. Recently, we discovered that the
α-phase survives at lower temperature with decreasing particle size [1]. For 10 nm silver iodide
nanoparticles, the α- to /-phase transition temperature was 40 °C. In this work, we havesynthesized small silver iodide quantum dots and investigated their phase transition behavior andionic conductivity.
The silver iodide quantum dots were synthesized by aliquid phase method. Silver nitrate and sodium iodide,and poly[N-vinyl-2-pyrrolidone] were used as the
precursors and the protective agent, respectively. The
transmission
showedthatelectronmicroscopy

obtainedquantum

(TEM)

image

dots

were

monodispersed and the mean diameter was estimatedto be 3.0 ± 0.7 nm (Figure inset). The powder X-ray
diffraction (PXRD) pattern suggested the formation ofsilver iodide quantum dots (Figure). From differential
scanning

calorimetry,

it

was

found

that

the

synthesized quantum dots have no phase transition of

Figure. PXRD patterns of bulk silver

silver iodide up to 250 °C. The ionic conductivity was

iodide and quantum dots (inset: TEM
image of silver iodide quantum dots)[2]

investigated by impedance analysis.
Reference(s)[1] R. Makiura, T. Yonemura, T. Yamada, M. Yamauchi, R. Ikeda, H. Kitagawa, K. Kato, and M.
Takata, Nat. Mater. 8 (2009) 476.
[2] T. Yamamoto, H. Kobayashi, and H. Kitagawa, Chem. Lett. Published online: DOI:
10.1246/cl.140409.

A26

Electronic structure and quantum effects

A new structural model for Al23– magic cluster:
A face-sharing bi-icosahedral motif
Kiichirou Koyasu1,2 and Tatsuya Tsukuda1,2
1
2

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

Metal clusters of Na, Al, and Au have been viewed as “superatoms” which accommodate valence
electrons in their discrete superatomic orbitals. High stability of magic clusters has been explainedby the closure of the electronic shells when the total number of valence electrons are 8, 18, 20, 34,
40,.... For example, magic clusters Al13– and Al23– observed in the gas phase have been viewed assuperatoms in which 40 and 70 valence electrons are accommodated within icosahedral andfcc-based cores (structure 1 in Fig. 1a), respectively [1]. In contrast, Au superatoms have beensynthesized by protection with ligands, such as thiolates (SR) and phosphines. The icosahedral
Au135+ superatomic core with 8 electrons is formed in Au25SR18– [2,3]. In addition, three types ofquasi-molecules made of two Au13 superatoms, Au239+, Au2511+, Au259+ with bi-icosahedral (bi-Ih)
motifs have been reported so far [4].
Motivated by the successful synthesis of bi-Ih Au clusters, we investigated the possibility that Al23–
takes a face-sharing bi-Ih structure by DFT calculations (B3LYP/6-311++G**). We found thatisomer 2 (Fig. 1b) with a bi-Ih motif is a local minimum structure, although it is less stable thanisomer 1 (Fig. 1a) by 0.97 eV. The vertical detachment energies, VDEs, of isomers 1 and 2 were
calculated to be 3.16 and 3.17 eV, respectively (Fig. 1). These VDE values are close to that
determined by photoelectron spectroscopy (3.57 eV)[5]. On the basis of these results, we propose a

(a)

(b)

face-sharing bi-ih motif as a possible structure of themagic cluster, Al23–. In order to gain an insight into
the bonding scheme between two Al13 superatoms,
we compared the shapes of molecular orbitals of
Al13– and Al23–. It is concluded that constructive
overlap of 1F and 2P superatomic orbitals ofdeformed Al13 (D3d) units is responsible for thebonding of two Al13 superatoms in Al23–.

ΔE
VDE

1
0.00 eV
3.16 eV20.97 eV
3.17 eVFig. 1 Optimized structures, relative–
stability (ΔE), and VDE for Al23 .

References[1] A. Aguado and J. M. López, J. Chem. Phys. 130 (2009) 064704.
[2] M. W. Heaven et al., J. Am. Chem. Soc. 130 (2008) 3754.
[3] Z. Manzhou et al., J. Am. Chem. Soc. 130 (2008) 5883.
[4] J. Nishigaki, K. Koyasu, and T. Tsukuda, Chem. Rec. in press, DOI: 10.1002/tcr.201402011.
[5] J. Akola et al., Phys. Rev. B 62 (2000) 13216.

A27

Electronic structure and quantum effects

Non-spherical gold clusters with the lowest-energy intense absorptions:strong correlation between geometric and electronic structures
Yukatsu Shichibu,1,2 Mingzhe Zhang,2 and Katsuaki Konishi1,212Faculty of Environmental Earth Science, Hokkaido University, Sapporo, Japan

Graduate School of Environmental Science, Hokkaido University, Sapporo, Japan

Subnanometer-sized gold clusters with gold atoms of ~10 have attracted considerable attention
because they are expected to show unique size- and/or structure-dependent physicochemical
properties.[1]While conventional monophosphine-ligated gold clusters favored sphericalgeometries and typically took on brownish colors,[2] we found that a series of non-spherical Aun
clusters (n = 6, 7, 8, 11) belonging to “[core+exo] motif” exhibit unusual absorption properties
during the systematic study on diphosphine-ligated gold clusters.[3-6]Fig.1 top shows geometric structures of [core+exo]-type [Au6(dppp)4]2+ (1), [Au7(dppp)4]3+ (2),[Au8(dppp)4Cl2]2+ (3) and [Au11(dppe)6]3+ (4) from single-crystal X-ray diffraction analyses (dppp =Ph2P(CH2)3PPh2, dppe = Ph2P(CH2)2PPh2).

Interestingly, the Au6 structure of 1 can beinterpreted as an elemental unit of 2 - 4 and the other Aun (n = 7, 8, 11) structures are described as
growth or fusion of the Au6.

Moreover, each of their absorption spectra exhibited thelowest-energy intense band in visible region (Fig.1 bottom). These isolated bands have neverbeen seen in the spectra of monophosphine-ligated gold clusters and were all assigned to simple
HOMO-LUMO intraband(6sp → 6sp) transitions
from density functional
theory (DFT) calculation.
So the attachment of
only one Au atom to apolyhedral

core

could

develop such an unusual
absorption.

The strong

correlation between the
shapes and electronic
structures of the clusters
is discussed from anelectron system (4e) andthe jellium model.

Figure 1. Skeletal structures and absorption spectra of Aun clusters(n = 6, 7, 8, 11; 1 - 4). Inset shows [core+exo] motif, in which one
or two exo Au atoms are attached to centered polyhedral Au cores.

References[1] T. Tsukuda, Bull. Chem. Soc. Jpn. 85 (2012) 151.
Chem. 32 (1984) 237.

[2] K. P. Hall, D. M. P. Mingos, Prog. Inorg.

[3] Y. Shichibu et al., to be submitted.

Inorg. Chem. 52 (2013) 6570.

[4] Y. Shichibu, K. Konishi,[5] Y. Shichibu, Y. Kamei, K. Konishi, Chem. Commun. 48 (2012)7559. [6] Y. Kamei, Y. Shichibu, K. Konishi, Angew. Chem. Int. Ed. 50 (2011) 7442.

Electronic structure and quantum effects

A28

Density functional theory study on hydrogen absorption properties ofnano-sized transition metal clusters (1):difference between Pd/Pt bulk and their clusters
Aya Matsuda and Hirotoshi Mori
Department of Chemistry and Biochemistry, Ochanomizu University, Japan[Introduction] Hydrogen storage is essential to utilize hydrogen energy in a practical manner.
Various kinds of hydrogen absorbing materials have been proposed. One of the best-knownhydrogen storage materials is bulk palladium (Pd). As the hydrogen absorption of bulk Pd startfrom H-adsorption on its surface, it has been expected that the hydrogen absorbing ability can be
improved by nanoparticulation. However, Yamauchi et al. experimentally showed that the simple
expectation is not correct, i.e. nano-sized Pd has lower hydrogen absorbing ability [1]. They also
found that platinum (Pt), which belongs to same group 10, does not shown any hydrogen
absorption in a bulk form and manifests hydrogen absorbing ability by nanoparticulation.
However, the origin of the differences of hydrogen absorption ability among these inorganic metal
systems has not been understood. The object in this study is to explain the differences of thehydrogen absorption properties from a theoretical point of view.
[Methods] A set of DFT calculations at the RI-PBE/def-SV(P) level of theory was performed toinvestigate electronic structures of Pd55, Pt55, bulk Pd, and bulk Pt. First, geometries of the
inorganic metal clusters were optimized with cubooctahedral (Oh) symmetry, which was observedin X-ray diffraction experiments [1,2]. As the crystal structure of bulk Pd and Pt have beenreported, we used the experimental parameters for electronic band structure calculation of thebulks. Then, using cubic grid points with an interval of 0.25 Å, interaction energies between an H
atom and Pd55, Pt55, bulk Pd and bulk Pt were evaluated.
[Results] The most stable hydrogen diffusion path predicted
for Pd55 is shown in Fig. 1. Similar path was also obtained for
Pt55. Our calculations show that the hydrogen in Pd55 is themore stable than that in Pt55. The results well correspond to
experimental observation by Yamauchi et al. The most stable
Fig. 1 The most stable Hhydrogen absorption site is octahedral (Oh) site, of which H
diffusion path in Pd55
absorption energies for Pd55 and Pt55 in Oh site are -0.54 eV
and -0.18 eV, respectively. To discuss the difference ofinteraction energy between absorbed H atom and M55 (M=Pd,
Pt), we decompose the interaction energy by their
physicochemical origins; electrostatic, repulsive, polarizableand dispersion interaction. The difference of repulsive
Fig. 2 The electron diffusioninteraction energy between Pd and Pt system is the largestof Pd6 (left) and Pt6 (right)(2.03 eV), which makes the difference of stability. It wasclarified that the instability of H atom in Pt55 is due to relativistic expansion of electronic distribution(Fig. 2). In the poster session, difference between cluster and bulk will be discussed in detail.
[References] [1] M. Yamauchi et al., J. Phys. Chem. C, 112, 3294 (2008) [2] M. Yamauchi et al.,Synth. Met., 135, 757, (2003)

Electronic structure and quantum effects

A29

Density functional theory study on hydrogen absorption properties ofnano-sized transition metal clusters (2):dependency on composition and internal structures
Kasumi Miyazaki, Aya Matsuda and Hirotoshi Mori
Department of Chemistry and Biochemistry, Ochanomizu University, Japan[Introduction] Hydrogen storage is essential to utilize hydrogen energy in a practical manner.
Promising materials for hydrogen storage are nano-sized transition metal clusters. It wasreported by Yamauchi et al. that nano-sized mixed transition metal (alloy) clusters show differenthydrogen absorbing properties from pure transition metal clusters. They also found that thehydrogen absorbing ability can be tuned by composition and internal structures of the mixed
metals, e.g. Pd/Pt alloy cluster of which composition of Pt is ca. 10% shows better hydrogen
absorption ability (0.40 H/M) [1] than pure Pd cluster (0.30 H/M) [2]. Although these experimental
observations anticipate the finding of novel materials for hydrogen storage, the mechanism for thetuning for hydrogen absorbing properties has not been well understood. Using density functional
theory calculations, recently, we studied the mechanism from a molecular level point of view. In
this presentation, we will discuss relationships among chemical composition, internal structure,electronic structure, and hydrogen storage property of nano-sized mixed transition metal clusters.
[Methods] A set of DFT calculations at the RI-PBE/def-SV(P) level of theory was performed toinvestigate electronic structures of Pd/Pt mixed clusters (Pd55, Pd50Pt5, Pd42Pt13, Pd28Pt27, andPt55). First, geometries of the clusters were optimized. For the mixed metal clusters, core-shell
type and solid-solution type structures were take into account. Interactions between an H and
the Pd/Pt mixed clusters were evaluated.
[Results]
A set of H-absorption interaction
potential energy curves along normal directions to(111) surface of Pd55, Pt55, and core-shell type
Pd42Pt13 are shown in Fig. 1. Our calculation
showed that all the clusters shown in this figure canabsorb an H atom inside, as observed
experimentally. Since the potential minima for Pt55
is much shallower than the others (and the positionof energy minima is just below the surface), it well
explain the fact that Pt nano particle can absorb H
atoms, but the amount of them is small (0.15 M/H).
It was also well explained that the core-shell typeFig. 1 H-absorption potential energy
Pd42Pt13 has similar H absorption property to thecurves for Pd55, Pt55, and core-shell
type Pd13Pt42 shown in r.h.s.
Pd55. Kobayashi et al. reported that adsorbed H
atoms distribute on the interface between Pt coreand Pd shell [3]. Our calculation reproduced their observation. In the poster session,
dependency on alloy composition will be discussed. The case of solid solution type cluster will bealso discussed.
[References] [1] H. Kobayashi et al., J. Am. Chem. Soc., 132, 5576 (2010) [2] M. Yamauchi et al.,J. Phys. Chem. C, 112, 3294 (2008) [3] H. Kobayashi et al., J. Am. Chem. Soc., 130, 1818 (2010)

A30

Electronic structure and quantum effects

Electronic shell closure of Al13 by electron donation from PVP
Tomomi Watanabe,1,2 Kiichirou Koyasu,1,2 and Tatsuya Tsukuda1,2
1
2

Department of Chemistry, The University of Tokyo, Tokyo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

Ligands play an important role in stabilizing metal clusters by steric protection and regulating thenumber of the electrons for the closure of electronic shells in the clusters [1]. For example, thenumber of valence electrons in the Au13 clusters protected by electron-withdrawing ligands suchas thiolates and halides is adjusted to be 8. In contrast, we can expect that Al13 clusters having 39
electrons can be electronically stabilized by donating one electron from the protecting ligands.
Polyvinylpyrrolidone (PVP) is a candidate for an electron donating stabilizer as demonstrated
experimentally [2] and theoretically [3] for stabilization of Au clusters. In this study, we
computationally investigated the stabilization of Al13 by electron donation from PVP.
N–Ethyl–2–pyrrolidone (EP) was used as model of PVP. Geometrical structures ofAl13(EP)n (n = 0–4) were optimized by DFT at the level of B3LYP/6-31G(d) using Gaussian 09
package. Global and local minima structures were confirmed by vibrational analysis. The binding
energy of the EP ligand (BE) and increment of the Mulliken charge on the Al13 core (Q) were
estimated.
The optimized structures of Al13(EP)1 are shown in
Table 1. In isomer 1, EP is bounded to Al13 throughthe carbonyl oxygen with a binding energy of 1.11

Table 1. The optimized structure, BE and Q of Al13 (EP) 1 .
Isomer 1

Isomer 2

BE (eV)

1.11

0.01

Q

–0.36

–0.02

eV, whereas EP is weakly bound to Al13 in isomer 2.
The electronic charge of Al13 core is increased by–0.36e in isomer 1, indicating that EP can act aselectron donating ligand to Al13. The second andOptimized
structure

third EP ligands also stabilized Al13 by electron
donation through carbonyl O atom. The Q value ofAl13(EP)3 was almost –1e. This indicates that theelectronic shell of Al13 is closed by electron donationfrom three EP ligands.
References[1] M. Walter et al., Proc. Natl. Acad. Sci. U.S.A. 105 (2008) 9157.
[2] H. Tsunoyama et al., J. Am. Chem. Soc. 131 (2009) 7086.
[3] M. Okumura et al., Chem. Phys. Lett. 459 (2008) 133.

A31

Electronic structure and quantum effects

Precise Separation of Metal Clusters Protected by Two-Types of Thiolate
Ligands
Yoshiki Niihori1, Miku Matsuzaki1, Chihiro Uchida1, and Yuichi Negishi1
1

Department of Applied Chemistry, Tokyo University of Science, Tokyo, Japan[Introduction] Thiolate-protected gold clusters have attracted a great deal of attention as new
functionalized nano-materials. It will be able to change their chemical/physical properties bychanging the surrounding ligands. However, in many cases, the synthesis of cluster with multiple
types of thiolate ligands results in a distribution of composition of the cluster-surface. To control
the function of the cluster by changing the composition ofcluster-surface, precise separation technique is required.
Herein we report precise separation of metal clusters
protected by two-types of ligands by use ofhigh-performance liquid chromatography (HPLC).
[Experiment] Au24Pd clusters protected by two-types ofthiolate ligands are synthesized by using ligand exchange
reaction with Au24Pd(SR1)18 and incoming thiol (R2SH) in
solution system. As-prepared Au24Pd(SR1)18-n(SR2)n (n =Figure 1. Comparison of (a) MALDI-MS
0-18) clusters were separated by using HPLC with reverseand (b) linear-gradient chromatogram ofphase column. To achieve precise separation, we applied
as-prepared cluster..

following
two-typesofgradient
programs.
1)
Linear-gradient program; the mobile phase was substituted
from methanol to THF linearly. 2) Step-gradient program;the mobile phase was substituted from methanol tomethanol/THF mixture intermittingly. In the chromatogram,each fraction were corrected and characterized withMALDI-Mass spectrometry.
[Result and Discussion] Figure 1 indicates thecomparison of MALDI-MS and linear-gradientchromatogram of as-prepared Au 24 Pd(SC 12 H 25 ) 18-n (SCH2PhtBu)n cluster. In MALDI-MS, each peak wereassigned to PdAu24(SC12H25)18-n(SCH2PhtBu)n with different
n. Figure 2 presents MALDI-MS of each corrected fractions.

Figure 2.
clusters.

MALDI-MSofseparated

We found that all the clusters with individual combination of
two-types of ligands were separated precisely.[1] Sameexperiment has been done by changing the combination of
two-types of thiolate/setenolate ligands and metal cores(Au25, Au38). We found that our method has generalversatility for separation of various metal clusters with
two-types of ligands. Figure 3 indicates step-gradientchromatogram of Au24Pd(SC2H4Ph)18-n(SC12H25)n cluster.
Several fine peaks were observed in Figure 3(a) andmultiple sub-peaks in one peak were observed. We
Figure 3. (a) Linear-gradient Chromatoattributed these sub-peaks to coordination isomers. Wegram and (b) expanded chromatogram
found that when a step-gradient used, it could be possible[2]of squared area in (a).
to separate clusters with higher resolution.
[1] Y. Niihori, M. Matsuzaki, T. Pradeep, Y.Negishi, J. Am. Chem. Soc., 135, (2013) 4946-4949.
[2] Y. Niihori, M. Matsuzaki, C. Uchida, Y. Negishi, Nanoscale, in Press, (2014).

Electronic structure and quantum effects

A32

Ultrafast photoelectron spectroscopy of metal clusters supported on MgOand Si substrates
Florian Knall,1 Mihai E. Vaida,1 Thorsten M. Bernhardt,1
Hisato Yasumatsu,2 and Nobuyuki Fukui3
1

Institute of Surface Chemistry and Catalysis, University of Ulm, Ulm, Germany
2

Cluster Research Laboratory, Toyota Technological Institute;

3

In East Tokyo Laboratory, Genesis Research Institute, Inc., Chiba, JapanThe dynamics of photoexcited electrons of metal clusters supported on ultrathin oxide films[1,2]and on Si(111) substrates[3] are discussed on the basis of time-resolved two photon
photoemission spectra measured at different wavelengths by means of a time-of-flight energy
analyzer in combination with a femtosecond laser. One- and two photon processes for thephoto-emission have been observed.
References[1] M.E. Vaida, T. Gleitsmann, R. Tchitnga, T.M. Bernhardt, J. Phys. Chem. C 113 (2009) 10264.
[2] M.E. Vaida, T. Gleitsmann, R. Tchitnga, T.M. Bernhardt, Phys. Status Solidi B 247 (2010)1139.
[3] H. Yasumatsu, T. Hayakawa, T. Kondow, Chem. Phys. Lett. 487 (2010) 279.

* This research was supported by JSPS Invitation Fellowship Program, Summer Program andPostdoctoral Fellowship, and the Special Cluster Research Project of Genesis ResearchInstitute, Inc.

A33

Electronic structure and quantum effects

Graphene-supported metal clusters: Well-defined nanostructures for theinvestigation of photo-induced processes
Kira Jochmann,1 Thorsten M. Bernhardt1
1

University of Ulm, Institute of Surface Chemistry and Catalysis, 89069 Ulm, Germany

During the last decade considerable attention was drawn to the growth of graphene on metal
single crystal surfaces, where it provides an ideal template for the ordered growth of regular metalcluster arrays. Building on various investigations about the detailed growth of these cluster
super-lattices, we make use of the possibility to easily grow nanostructures with equally spaced
and mono-disperse clusters for fundamental research in laser selective photochemistry.
Our new experimental setup enables time-resolved measurements due to a femtosecond laser
system on the one hand and surface analysis via scanning tunnelling microscopy on the otherhand. In first light interaction measurements time-resolved two-photon photoemission
spectroscopy (2PPES) was applied to gain an insight into the unoccupied electronic structure of
the Ir(111)/graphene/Ir cluster system at different graphene and cluster coverages. In subsequent
experiments the combination of femtosecond laser pump-probe mass spectrometry withresonanceenhancedmulti-photon

ionization

and

STM

will

be

employedtorevealphoto-dissociation dynamics of our probe molecule methyl bromide with spatio-temporal
resolution.

Electronic structure and quantum effects

A34

Properties of designed small gallium-nitride clusters
Tibor Höltzl1
1

Furukawa Electric Institute of Technology, Budapest, Hungary

Geometry and electronic structure of small gallium-nitride clusters was investigated using
quantum chemical methods. Most of the nano-scale studies focus on the difference between themacroscopic and the nano-scale materials. In contrast, our work emphasizes the flexibility of thenano-design which aims to construct structures with desired properties. Our goal was to constructgallium-nitride clusters with similar geometric structure to the bulk material.
We have found that simple design principles (which are adapted based on the publications ofsphalerite indium-phosphide) can be successfully used to design various cluster sizes with thedesired properties. The underlying method is simple: the coverage of the surface of the cluster isthe most important factor which determines the electronic and the geometric structure. The cluster
has to be covered such that every atom in it must participate in four chemical bonds from which
one and only one is dative, while the remaining ones are covalent.
The applicability of this principle for GaN clusters was supported by our computation of thecanonical phase diagram of a small and a larger cluster with different coverages.
The clusters constructed using the previous methods can be used to study various physical andchemical phenomena and to build model systems. Geometrical structure of even a small cluster isclose to that of the bulk gallium nitride, and interestingly, the specific heat per GaN units of verysmall clusters is also similar.
Also, the surface modification of the gallium nitride clusters opens the way toward small clusters
with the desired properties. Clusters with several different coverages and reaction sites wereconstructed and investigated. The chemical behavior of these reaction sites is highly different. On
one site this shows that the surface modification of these type of clusters can be applied to obtaina desired chemical behavior, which would be useful e.g. in catalyst design. On the other hand, italso emphasizes the importance of the role of the chemical bonding around the gallium reaction
site, also in a larger system. This could also influence the surface growth of the bulk.

Electronic structure and quantum effects

A35

Stabilization of Magic-Numbered Au25(SR)18 Cluster
Wataru Kurashige,1 Masaki Yamaguchi,1 Katsuyuki Nobusada,2 and Yuichi Negishi1
1

2

Department of Applied Chemistry, Tokyo University of Science, Tokyo, Japan
Department of Theoretical and Computational Molecular Science, Institute for Molecular Science,
Okazaki, Japan

1. Introduction
Small gold clusters protected by ligands are of interest in
both fundamental and applied research because they
exhibit size specific optical and physical properties. Of
such clusters, thiolate-protected gold clusters (Au:SR),
especially Au25(SR)18 has been the most extensively
studied. Recently, we have attempted to synthesized
more stable clusters than Au25(SR)18 (Fig. 1). In
consequence, we succeeded in synthesizing a
thiolate-protected Au24Pd(SR)18 cluster, which is amono-Pd-doped cluster of Au25(SR)18 and aselenolate-protected Au25(SeR)18. We compared theirFig. 1. Our object
stability with those of Au25(SR)18. The results indicatedthat Pd doping and selenolate protection increase a stability of the cluster against the degradation
in solution.
2. ExperimentThiolate-protected PdAu24(SR)18 (1) was isolateted by Brust method and reverse phase HPLC and
Selenolate-protected Au25(SeR)18 (2) was isolated by that and solvent extraction. These isolated
compounds were characterized by UV-vis spectrum, ESI, MALDI, LDI mass spectrum, TGA, TEM
image, X-ray diffractogram and X-ray photoelectron spectra. And we investigated these stability insolution by pursuing time dependence of UV-vis spectrum.
3. Results and discussion
Only one peak was observed in the MALDI mass spectrum of 1, assigned to Au24Pd(SR)18 [1]. On
the other hand, only one peak was observed in the ESI mass spectrum of 2, assigned toAu25(SeR)18 [2]. These results indicate that these clusters were isolated in high purity using our
methods. Regarding stability in solution between Au25(SR)18 and Au24Pd(SR)18, the relative ion
intensity of Au25(SR)18 decreases over time, and after 30 days the mass spectrum exhibits only thepeak attributed to Au24Pd(SR)18. And we also did similar experiment between Au25(SR)18 andAu25(SeR)18. The absorption spectrum of Au25(SR)18 changed gradually over time, whereas that ofAu25(SeR)18 exhibited only a slight change, even after two days. These results indicate that
Au24Pd(SR)18 and Au25(SeR)18 are more stable than Au25(SR)18 in solution[3], [4].
Reference(s)[1] Y. Negishi, W. Kurahige, Y. Niihori, T. Iwasa and K. Nobusada, Phys. Chem. Chem. Phys., 12(2010) 6219.
[2] Y. Negishi, W. Kurahige and U. Kamimura, Langmuir (Letter), 27 (2011) 12289.
[3] W. Kurahige, M. Yamaguchi, K. Nobusada and Y. Negishi, J. Phys. Chem. Lett., 3 (2012) 2649.
[4] Y. Negishi, W. Kurahige, Y. Niihori and K. Nobusada, Phys. Chem. Chem. Phys. (Perspective),
15 (2013) 18736.

Electronic structure and quantum effects

A36

Theoretical Study on the Ln Dependence of Ln(COT)2 Photoelectron Spectra
Erika Nakajo, Tomohide Masuda, and Satoshi Yabushita
Department of Chemistry, Keio University, Yokohama, Japan
Lanthanide (Ln) complexes are attractive for their novel properties originating from the core-like
open-shell 4f orbitals. The sandwich cluster Ln(COT)2, consisting of Ln metal and
1,3,5,7-cyclooctatetraene (COT) ligands with the D8h symmetry is an important synthetic unit
towards the multiply-layered structures which have a great potential as magnetic and opticalnanowires. We have theoretically analyzed the electronic structure of a series of Ln(COT)2andthe corresponding neutral complexes, to simulate the recently reported anion photoelectron
spectra[1]. Fig. 1 shows the orbital interaction scheme of Gd(COT)2. The valence MOs with theenergy order e1g < e1u < e2g < e2u consist mainly of the COT  orbitals (L and L). Compared to the
COT orbitals, the large energy gap between e2u and e2g, and the level inversion of e1g and e1u on
sandwiching are both simply attributed to the symmetrically allowed mixings with the Ln 5d and 5p
orbitals. However, to explain the Ln dependence of these MO energies (Fig.2), several
complicated factors should be considered: (1) the shortening of the Ln-COT distance resulting
from lanthanide contraction, (2) the very strong intramolecular electrostatic interaction in the ionicbonding system[2], and (3) the covalent orbital interaction. Interestingly, even with the shorteningof the Ln-COT distance, the metal-ligand orbital overlaps remain constant or even decrease due tothe simultaneous contraction of the Ln atomic orbitals. Although the Ln 4f orbitals have little
contribution to the metal-ligand covalency, they are known to contribute to the stabilization ofneutral Ln(COT)2 through a specific metal-ligand interaction[3]. Because of the non-negligible
magnitude of the orbital overlap (from 0.05 in Ce to 0.02 in Yb), configuration interaction involving
4f(e2u) and the ligand L(e2u) occurs in a spin-dependent manner. For middle-range Ln, thisinteraction was indeed observed as the splitting of the X peak in the anion PE spectra that
correspond to the photodetachmentfrom the HOMO (e2u) [1]. The Ln
dependence of this interaction is
explained with a simple model relevantto the 4f configuration, with taking into
account the energy difference and theoverlap between 4f(e2u) and the ligand
L(e2u). The experimentally observed X
peak splittings thus have been proved
as an interesting example that shows
the remarkable interaction between theLn 4f and the ligand electrons.
Fig.1: Qualitative orbital interaction
Fig.2: Valence orbital energies
scheme of Gd(COT)2

[1] N. Hosoyal, K. Yada, T. Masuda, E. Nakajo, S. Yabushita, and A. Nakajima, J. Phys. Chem.
A 118 (2014) 3051.
[2] R. Takegami, N. Hosoya, J. Suzumura, A. Nakajima, and S. Yabushita, J. Phys. Chem. A
109 (2005) 2476.
[3] W. Liu, M. Dolg, and P. Fulde, Inorg. Chem. 37 (1998) 1067.

A37

Biotechnological and medical applications: imaging and sensors

Functionalized Gold Nanoclusters as Site-Specific Labels for Imaging ofEnteroviruses
Kirsi Salorinne,1 Varpu Marjomäki,2 Tanja Lahtinen,1 Mari Martikainen,2 Jaakko Koivisto,1 Sami
Malola,3 Mika Pettersson,1 and Hannu Häkkinen1,3
1
2

Department of Chemistry, Nanoscience Centre, University of Jyväskylä, Finland

Department of Biology and Environmental Sciences, Nanoscience Centre, University of
Jyväskylä, Finland3

Department of Physics, Nanoscience Centre, University of Jyväskylä, Finland

Monolayer protected gold nanoclusters of a few nanometers in size have proven to be promisingsite-specific labels for various biomolecules due to their unique properties that come from thesmall size and molecule-like characteristics that can be studied e.g. by transmission electron
microscopy (TEM).[1-4] In addition, by properly designing the protecting monolayer to include
specific linker molecules to allow site-specific conjugation to biomolecules, this technique enables
the investigation of different mechanisms or pathways of complex biomolecules, or tracking of thebiomolecule-gold cluster conjugates inside cells using the appropriate imaging technique. Here we
describearecentsuccess

inlabelingofenteroviruses

for

TEM

studiesbymaleimide-functionalized Au102(pMBA)44 clusters (pMBA = para-mercaptobenzoic acid).[5]Reference(s)[1] C. J. Ackerson, R. D. Powell and J. H. Hainfeld, Method Enzymol. 481 (2010) 195.
[2] C. J. Lin, C. Lee, J. Hsieh, H. Wang, J. K. Li, J. Shen, W. Chan, H. Yeh and W. H. Chang, J.
Med. Biol. Eng. 29 (2009) 276.
[3] T. Tsukuda, Bull. Chem. Soc. Jpn. 85 (2012) 151.
[4] H. Qiang, M. Zhu, Z. Wu and R. Jin, Acc. Chem. Res. 45 (2012) 1470.
[5] V. Marjomäki, T. Lahtinen, M. Martikainen, J. Koivisto, S. Malola, K. Salorinne, M. Petterssonand H. Häkkinen, Pros. Natl. Acad. Sci. 111 (2014) 1277.

Biotechnological and medical applications: imaging and sensors

A38

Metal nanoparticle modified electrochemical electrodes for nonenzymehydrogen peroxide sensing
Jue Wang1, Xuejiao Chen1, Kaiming Liao1, Guanghou Wang2 and Min Han1
1

National Laboratory of Solid State Microstructures and Department of Materials Science andEngineering, Nanjing University, Nanjing 210093,China
2
National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University,
Nanjing 210093, China
Rapid, accurate, stable, sensitive and low cost detection of H2O2 is very important in various fields
including clinical diagnostics, environmental analysis and food industry [1–3]. Dense metal(palladium, silver) nanoparticle arrays coating on glass carbon electrodes (GCEs) with gooddispersity were fabricated by using gas phase cluster beam deposition. The nanoparticle modified
electrodes show enhanced electrocatalytic activity toward the reduction of H2O2 with a very low
overpotential [4]. With an optimized nanoparticle coverage, a high selective nonenzyme sensing
platform for stable detection of H2O2 with a low detection limit (1×10-7 M), high sensitivity(5.65×10−1AM−1CM-2) as well as a wide linear range from 1.0×10−6 to 6.0×10−3M was realized. The
electrodes also show a very quick response to the concentration change of H2O2, with a current
rise time of less than 1 s, which is faster than all the silver or palladium based electrodes.
References[1] S.A. Kumar, S.F. Wang and Y.T. Chang, Thin Solid Films 518 (2010) 5832–5838.
[2] G.H. Zhang, N.B. Yang, Y.L. Ni, J. Shen, W.B. Zhao and X.H. Huang, Sensors and Actuators B:
Chemical 158 (2011) 130–137.
[3] M. Delvaux, A. Walcarius and S. Demoustier-Champagne, Analytica Chimica Acta 525 (2004)
221–230.
[4] K.M. Liao, P. Mao, Y.H. Li, Y.L. Nan, F.Q. Song, G.H. Wang and M. Han, Sensors and Actuators
B: Chemical 181 (2011) 125–129.

Fig.1. (a) TEM image of the Pd clusters deposited on amorphous carbon film surface. (b) The
linear sweep stripping voltammetry (LSSV) measurements of the Pd NPs/GCE with different
nanoparticle coverage in 0.01M H2O2 (0.05M PBS, pH=7.4) at the scan rates of 0.05V/s. (c) The
amperometric responses of the Pd NPs/GCE with different nanoparticle coverage deposition times
upon successive addition of H2O2 into gently stirred 0.05 M PBS (pH 7.4) at −0.11V.

Biotechnological and medical applications: imaging and sensors

A39Gold Nanorod Assisted Laser Desorption/Ionization of Oligopeptides
Masanori Fujii,1 Naotoshi Nakashima,1,,2,3 and Yasuro Niidome1,2,4
1

Department of Applied Chemistry, Kyushu University, Fukuoka, Japan
2

I2CNER WPI, Kyushu University, Fukuoka, Japan
3

4

CREST, Tokyo, Japan

Kagoshima University, Kagoshima, Japan (Present Affiliation)

In Surface Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (SALDI-MS),nanostructured surfaces absorb photons and assist in desorption and ionization of sample
molecules. We have been reported highly efficient SALDI processes using gold nanorods on an
ITO plate previously1,2). Here, we controlled the aggregation of gold nanorods, and evaluated their
SALDI efficiencies.
Gold nanorods with aspect ratios of about 5 (51 ± 7 nm and 9.7 ± 1.1 nm in longitudinal andtransverse directions, respectively) were coated with poly(sodium styrenesulfonate) (PSS) anddeposited on an ITO plate. ITO plates were repeatedly immersed in a PSS-nanorod solution tocontrol the degree of aggregation of the gold nanorods. The nanorod-ITO plates were used for
SALDI-MS measurements to detect an oligopeptide (angiotensin I) cast on the plates. A
MALDI-MS machine (Autoflex III, Bruker Daltonics) was used for the mass spectrometry.
Fig. 1 shows the S/Ns of the mass signals plotted against the full width at half maximum (FWHM)
of longitudinal SP bands for gold nanorods on the ITO plates. For the plates showing 250-350 nm
SP bandwidths, the SALDI efficiencies depended on which spots were chosen for the mass
spectrometry to be performed at. Intense signals were randomly obtained, which strongly
suggested that there were a few extraordinary spots that showed highly efficient SALDI processes.
In the case of plates that the FWHM values were250-350, SEM observation indicated that small
aggregates, consisting of a few nanorods, formed on theplates. Image analysis of the SEM images showed thatthe efficient SALDI processes originated from small
aggregates consisting of 3 to 8 nanorods. Isolated gold
nanorods and large aggregates of nanorods did notshow efficient SALDI processes. The longitudinal SP
bands of the gold nanorods could be used as anindicator
toobtainthesize-controlled Fig. 1 S/Ns for the mass signals of angiotensin
I plotted against the FWHM of longitudinal SP
nanorod-aggregates. This approach should be bands for gold nanorods on the ITO plates.
advantageous for the preparation of highly sensitive andreproducible SALDI plates.
Reference[1] Y. Nakamura, Y. Tsuru, M. Fujii, Y. Taga, A. Kiya, N. Nakashima and Y. Niidome, Nanoscale3(2011)3793.
[2] M. Fujii, N. Nakashima, T. Niidome, and Y. Niidome, Chem. Lett., 43(2014) 131.

Biotechnological and medical applications: imaging and sensors

A40

Spontaneous Formation of Gold Glyconanoparticles by Direct Reaction of
ω-Glycosilated Alkylsulfanylanilines and HAuCl4
Ryuich Takegawa, Satoaki Onitsuka, Toshiyuki Hamada, Jun-ich Kurawaki, and Hiroaki Okamura
Department of Chemistry and Bioscience, Graduate School of Science and Engineering,Kagoshima University, Kagoshima, Japan
Gold glyconanoparticles were easily prepared by simply mixing HAuCl4 and ω-glycosilated
alkylsulfanylanilines in methanol. The 1H NMR and absorption spectra and TEM images of theresulting nanoparticles indicated the formation of aggregated nanoparticles that were covered withsugar molecules. The specific and reversible interaction of the glyconanoparticles and lectin
protein (concanavalin A, Con A) was also confirmed.
We have earlier reported a new
methodtopreparestablegold

nanoparticles covered with a single
organic species using HAuCl4 andN-acylbenzenethiol,

wherebenzenethiol acts as a “reductive
stabilizer” that reduces the Au3+ ion
and stabilizes the resulting gold
nanoparticles by coordinating to their

Scheme 1

Plausible structure of gold glyconanoparticle

surfaces [1].
Using this result, we developed new reductive stabilizers, ω-glycosilated alkylsulfanylaniline 1a-c,
which spontaneously afforded gold glyconanoparticles when mixed with HAuCl4 in methanol. The
expected pathway to form the gold glyconanoparticle and its plausible structure are shown in
Scheme 1. The absorption spectrum and TEM image of the resulting deep-blue solution clearly
indicated the formation of aggregated nanoparticles, which may be constructed by interparticle
hydrogen bonding of the surface sugar
moiety (Fig. 1).
The specific and reversible interaction of theglyconanoparticle 2c-AuNp and Con A wasconfirmed by the formation of an orange
precipitate of the 2c-AuNp-Con A aggregate,
which was dissolved by the subsequent
addition of mannose.
Reference

Fig. 1 Absorption of spectra (left) and TEM image (right,
scale bar 100 nm) of 2a-AuNp[1] H. Okamura, J. Kurawaki, T. Iwagawa, T. Hamada, M. Kawashima, Chem. Lett. 39 (2010)1258-1260.

Biotechnological and medical applications: imaging and sensors

A41

Nanopore devices for rapid structural analysis of Nanomaterials
Sou Ryuzaki,1 Masateru Taniguchi,2 Koichi Okamoto,1 and Kaoru Tamada1
1

Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, Japan
2

The Institute of Scientific and Industrial Research, Osaka University, Osaka, Japan

Rapid structural analysis methods for biomolecules consisting of single or several molecules insolution represent innovative technologies to reveal their functions because the functions strongly
depend on their own structures. However, there presently exist no rapid structural analysis
methods for single nanomaterials in solutions.

Nanopore technologies have the capacity toinvestigate the volume and shape of single nanomaterials in solutions owing to changes in ioniccurrents passing through the nanopores. Nanopores must have high spatial and time resolutions
to determine the structures of single nanomaterials.
Here we report the development of low-aspect-ratio nanopores with a spatial resolution of 35.5 nm
and a fast current amplifier, resulting in realization of ultrafast time resolutions of 1.0 μs.
Combining state-of-the-art technologies with multiphysics simulation methods to translate ioniccurrent data into structures of nanomaterials passing through a nanopore, we have achieved rapid
structural analysis of single gold nanorods, single polystyrene (Pst) beads, and single
dumbbell-like Pst beads in aqueous solutions. The present nanopore devices will be innovativetechnologies for the fields of nanobiodevices and structural biology.

Figure 1. Schematic illustration of the present structural analysis method using a nanopore. A
low aspect ratio nanopore is capable of structural analysis like a 3D scanner because the shape ofion current blockade due to a material translocation in a nanopore reflects the tomograms of thematerial passing through the nanopore.

A42

Structure and thermodynamics

Silver acetylide nano helical structure induced by impurities
Shota Ito,1 Yoshikiyo Hatakeyama,1 and Ken Judai1
1

Department of Physics, College of Humanities and Sciences, Nihon University, Tokyo, Japan

Silver tolylacetylide does not have chiral center carbon, and is an achiral molecule. However, itturned out that twisted nano ribbon structures, chiral helices, were generated by recrystallization insolution phase. We have investigated for the chiral origin how the achiral molecules aggregate to
the chiral nano helical structure. The solvent for recrystallization was changed between methanol,
ethanol, 1-propanol, and 1-butanol systematically. Fast recrystallization solvent such as methanol
was observed as twisted nanoribbon structures, and the other side, slower solvent such as
1-butanol was as straight non-twisted nanoribbon structures. Helical and non-helical structures
can be controlled by recrystallization solvent. Crystallization speed, in other words, quality of
crystal by crystallization kinetics is important for twisted nanoribbon structure [1].
An additional experiment showed that lightirradiation made solution color changing to
red and enhancement of twisting nanoribbon
structures. The light irradiation produced
decompositionofsilveracetylideanddimerization reaction. The dimerization ofacetylideindicatedredcolor,

anddisplacement of crystal by the decomposedcompounds enhanced crystal tension andtwisting.
Reference[1] K. Judai, Y. Hatakeyama, and J. Nishijo,
J. Nanosci. (2013) 545430.

Figure: Scanning Electron Microscopy (SEM) imageof twisted silver tolylacetylide.

Structure and thermodynamics

A43

Rapid cooling of isolated small carbon cluster anions
Takeshi Furukawa,1 Naoko Kono,1 Gen Ito,1 Jun Matsumoto,2 Hajime Tanuma,1Toshiyuki Azuma,3 Klavs Hansen,4 and Haruo Shiromaru2
1
2
3

Department of Physics, Tokyo Metropolitan University, Tokyo, Japan

Department of Chemistry, Tokyo Metropolitan University, Tokyo, Japan

Atomic, Molecular and Optical Physics Laboratory, RIKEN, Saitama, Japan
4

Department of Physics, University of Gothenburg, Gothenburg, Sweden

For vibrationally excited molecules, radiative cooling is usually a rather inefficient cooling pathway.
We have found that even-numbered carbon cluster anions radiate significantly faster than
odd-numbered ones, and much faster than by infrared (IR) radiation. Chain-form neutral carbon
clusters have filled or half-filled degenerate highest  orbitals depending on the parity. This is theorigin of the even/odd alternation in the electron affinities. It will also be reflected in the excitation
spectra of the anions, and in the even/odd alternation in the radiative cooling of small carbon
cluster anions.
The experiments were performed using the electrostatic ion storage ring at TMU, where weobserved time-resolved electron emission from C4-7 － anions on the timescale of a hundred
microsecond and longer after laser excitation [1]. The decays were observed to be thermal. For
C5－ and C7－, the time profile of the emission rate in the delayed reaction shows that the anions
were cooled slowly by IR radiations (timescale: tens of millisecond). On the other hand, theelectron emission rate of C4－ and C6－ after laser excitation decreased anomalously fast, on lessthan a few tens of microseconds. By comparing the calculated emission rates, we concluded that
this process was due to the electronic transitions via low-lying electronic excited states after the
inverse internal conversion (IIC) process, i.e., the conversion of energy from vibrationally excitedstates to electronically excited states. Although this IIC process is usually suppressed due to thesmall statistical weight of the excited state, it may dominate the cooling dynamics for isolated
molecules. It should be noted that IIC-accelerated cooling of trapped ions has so far been foundonly for large molecular ions (e.g. anthracene cation [2]) and the fast cooling of C4,6－ shows thatthe mechanism is present also for very small ions. For the evolution of interstellar molecules,
where two-body collisions produce highly excited products and radiative cooling determines
whether they survive intact, the IIC process will be more important for smaller molecules.
References[1] M. Goto et al., J. Chem. Phys. 139 (2013) 054306; K. Najafian, et al., J. Chem. Phys. 140(2014) 104311; G. Ito et al., Phys. Rev. Lett. 112 (2014) 183001.
[2] S. Martin et al., Phys. Rev. Lett. 110 (2013) 163003.

Structure and thermodynamics

A44

Radiative cooling of laser-heated niobium clusters
Klavs Hansen,1 Yejun Li,2 Vladimir Kaydashev,2 and Ewald Janssens2
1
2

Department of Physics, University of Gothenburg, 41296 Gothenburg, Sweden

Laboratory of Solid State Physics and Magnetism, KU Leuven, 3001 Leuven, Belgium

Thermal radiation and thermionic emission have been established as important decay channels ofhighly excited clusters that are made of refractory materials [1,2]. In most materials, the activationenergy for evaporation of a massive fragment (atom or molecule) is lower than the ionizationenergy, which strongly favors loss of atoms in unimolecular reactions. For refractory materials, thehigh binding energy makes the thermionic emission channel competitive and also radiative cooling,i.e., thermal emission of photons, appears on the timescale (about 100 μs) defined by molecularbeam devices [3]. Thermal photon emission is not an activated process and is only suppressed
relative to atomic evaporation due to the large frequency factor of the latter. This is different at low
energy where a crossover from atomic evaporation or thermionic emission to radiative cooling
occurs.
Clusters of niobium are known to emit atoms, electrons, and photons in thermal processes on the
nano- and microsecond timescales [4]. Only a few experimental studies tried to quantify theradiation emitted by recording the black-body radiation spectra of laser-heated clusters and ofclusters heated by oxidation [5].
In the present work, we study for the first time the competition between atomic evaporation andthermionic emission as decay channels of excited size-selected refractory metal clusters. The
radiative cooling of small laser-heated Nbn+ (8 ≤ n ≤ 22) clusters has been measured. The emitted
power was determined by the quenching effect on the metastable decay, employing two different
experimental protocols. The radiative power decreases slightly with cluster size and shows nostrong size-to-size variations. The magnitude is 40-50 keV/s at the timescale of several
microseconds, which is the measured crossover time from evaporative to radiative cooling.
Reference(s)[1] G. Ganteför et al., Phys. Rev. Lett. 77 (1996) 4524.
[2] Y. Toker et al., Phys. Rev. A 76 (2007) 053201.
[3] K. Hansen and E.E.B. Campbell, J. Chem. Phys. 104 (1996) 5012.
[4] V.J.F. Lapoutre et al., J. Chem. Phys. 139 (2013) 121101.
[5] U. Frenzel et al., Z. Phys. D 40 (1997) 108.

Structure and thermodynamics

A45

Adsorbing carbon dioxide on fullerenes at 0.37K under the influence of charge:a mass spectrometric and molecular dynamics/DFT study
Stefan Ralser1, Johannes Postler1, Alexander Kaiser1, M. Probst1, S. Denifl1, Diethard K. Böhme2,
and Paul Scheier1
1Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Austria
2

Department of Chemistry,York University, Toronto, ON, Canada M3J 1P3

In the current era of climate change, it is essential to know and to understand the basic propertiesof constituents involved in this phenomenon. Especially the binding of greenhouse gases tosuitable materials is of particular interest to find efficient sinks that will reduce the amount of such
substances in the atmosphere [1]. In the present study, we focus on the greenhouse gas carbon
dioxide and its adsorption properties on carbonaceous materials. In this context, various materials
including graphites, graphenes and nanotubes have been explored [2, 3, 4]. Here we report theadsorption of CO2 on neutral and charged buckminster fullerenes (C60).
C60, together with CO2 is embedded in superfluid helium nanodroplets at 0.37K via a pickup
process. Electron collisions with the doped He nanodroplets results in charged complexes of theform C60(CO2)n that are analyzed utilizing mass spectrometry.
For cationic clusters significantly more CO2 molecules can be accommodated in the first shellaround the C60 fullerene. According to molecular dynamic simulations and DFT calculations, thisgain results from a reorientation of the CO2 axis with respect to the center of the positively charged
C60. Mass spectrometrically determined shell closures are 35 and 48 for the anions and cations,
respectively which agrees very well with the calculated shell closures. The first shell of CO2
around a neutral C60 contains 44 molecules according to our simulations.
This work was supported by the FWF, Wien (P23657, I978 and P26635)
References[1] D.M. D’Alessandro, B. Smit and J.R. Long, Angew. Chem. Int. Ed.49 (2010) 6058-6082[2] E.J. Bottani, V. Bakaev and W. Steele, Chem. Eng. Sci. 49 (1994) 2931-2939[3] A. Kumar M.S. Ramaprabhu, AIP Advances 1 (2011) 032152[4] M. Cinke et. al., Chem. Phys. Lett. 376 (2003) 761-766

A46

Structure and thermodynamics

Entropy-driven isomer switching in Fe+(H2O)nprobed with IR spectroscopy and free-energy calculations
Kazuhiko Ohashi,1 Jun Sasaki,1 Gun Yamamoto,1
Ken Judai,2 Nobuyuki Nishi,2 and Hiroshi Sekiya1
1

Department of Chemistry, Kyushu University, Fukuoka, Japan
2

Institute for Molecular Science, Okazaki, Japan

We have investigated coordination and solvation structures of metal ions through gas-phase
spectroscopy. For Fe+(H2O)n (n = 3–8), we already reported IR photodissociation spectra in the
OH stretch region [1]. The spectral features were consistent with isomers with 2-fold linear
coordination, but they were not lowest in energy from DFT calculations. We aim at resolving thediscrepancy by considering temperature (entropy) effects on isomer distributions of Fe+(H2O)n.
Geometries of Fe+(H2O)n were optimized and harmonic vibrational frequencies were computed at
the B3LYP/6-311+G(2df) level by using GAUSSIAN 09 package. Partition functions and then freeenergies of low-lying isomers were evaluated under rigid-rotor/harmonic-oscillator approximation.
Here we focus on Fe+(H2O)8; figure displays the optimized geometries and free energies of threeisomers of Fe+(H2O)8 with a coordination number of 2, 3, and 4. (4+4) is lowest in free energy at
T = 0–75 K. The ordering of (4+4) and (2+4+2) inverts at 75 K and that of (4+4) and (3+5) at 200
K. (2+4+2) becomes increasingly stable with increasing temperature. At 250–300 K, (4+4) and(3+5) are higher in free energy than (2+4+2) by 24–31 and 19–21 kJ mol–1, respectively.
At lowest T, (4+4) should be dominant, because it is favorable in enthalpy. Meanwhile, (2+4+2)
has a larger number of lower-frequency vibrations than (4+4), because outer-shell waters arebound less rigidly; their contribution to entropy is rather large. Owing to the entropy effect,(2+4+2) becomes abundant at higher T. We conclude that IR observation of 2-coordinatedisomers is reasonable, because T = 250–300 K is estimated for Fe+(H2O)5–8 under investigation.
20

G / kJ mol

-1

(4+4)

: Fe+

: H2O

0

(3+5)

-20
-40

(4+4)

(2+4+2)
-60

(3+5)
0

100

200 300
T / K

400

500

(2+4+2)+

Fig. Optimized geometries for three isomers of Fe (H2O)8 and free energy of (2+4+2)
and (3+5) relative to (4+4) as a function of temperature in the 0–500 K range.

[1] K. Ohashi et al., ISSPIC XVI (2012) A30.

Structure and thermodynamics

A47

Syntheses of Au@PdAg and Au@PdAg@Ag core–shell Nnanorods throughdistortion induced alloying between Pd shells and Ag atoms over Au nanorods
Masaharu Tsuji,1,2,3 Koichi Takemura,2 Chihiro Shiraishi,2 Keiko Uto,1 Atsuhiko Yajima,3Masashi Hattori,1 and Takeshi Daio4
12

Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Japan

Department of Applied Science for Electronics and Materials, Kyushu University, Kasuga, Japan
3
4

Department of Automotive Science, Kyushu University, Kasuga, Japan

International Research Center for Hydrogen Energy, Kyushu University, Fukuoka, Japan

Nobel Au@PdAg and Au@PdAg@Ag core–shell nanorods (NRs) having PdAg alloy shells weresynthesized using Au@Pd NRs as seeds. Their crystal structures and growth mechanisms were
examined using transmission electron microscopic (TEM), TEM–energy dispersed X-ray
spectroscopic (EDS), XRD, ultraviolet (UV)–visible (Vis)–near infrared (NIR) extinction
spectroscopic data. In the first step, rectangular or dumbbell-type Au@Pd seeds were prepared by
reducing H2PdCl4 with ascorbic acid in an aqueous solution in the presence of Au NRs as seeds
and cetyl trimethyl ammonium bromide (CTAB).1 In the second step, when Ag+ ions were reducedwith ascorbic acid and CTAB in the presence of rectangular or dumbbell-type Au@Pd NRs as
seeds and CTAB, Au core PdAg alloy shells were formed with maximum Ag contents of about 16
or 24%, respectively, after 10 min heating at 60 °C. The driving force of alloying between Pd shells
and Ag atoms is distortion of Pd layers over Au NRs on the basis of peak shifts and broadening of
XRD data. At longer reaction times over 10 min, the content of Ag exceeds its maximum solubility
in Pd shells, and then the second Ag shells were epitaxially grown over Au@PdAg NRs via asingle island-growth mechanism. In this mechanism, crystal growth of Ag shells over Au@Pd-Ag
cores starts from the formation of single nuclei on a wide side PdAg alloy facet followed by growth
to one rectangular rod shell and further growth of neighboring rectangular rod shells having {100}facets, as shown in Fig. 1.

Fig. 1. TEM-EDS images and growth mechanism of rectangular Au@PdAg@Ag nanorod.
Reference[1] M. Tsuji, K. Ikedo, K. Uto, M. Matsunaga, Y. Yoshida, et al., CrystEngComm, 15 (2013) 6553.

Structure and thermodynamics

A48

Ligand-protected gold clusters with novel interfacial structures
Prasenjit Maity,1 Jun-ichi Nishigaki,1 Tatsuya Tsukuda1,2
1
2

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

We present two topics on development of new ligand-protected Au clusters by controlling theinterfacial structures.
1. Protection of Gold Clusters by Bulky Thiolates [1, 2]
Bulky arenethiols, EindSH (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) and DppSH (Dpp
= 2,6-diphenylphenyl), were used as protecting ligands with an aim to suppress the formation of–SR–[Au(I)–SR–]n oligomers on the Au core. Au41(SEind)12 and Au25(SDpp)11 were obtained bymixing of the hydrosol of small (diameter<2 nm) PVP-stabilized Au clusters and the toluene
solution of the corresponding thiol and subsequent etching process. As expected, the ligand-to-Au
ratios of Au41(SEind)12 and Au25(SDpp)11 are significantly smaller than those of Au:SR reported sofar. Structural characterization of these isolated clusters suggests that the bulky thiolates arebonded directly to the surface of Au41 with twisted pyramidal motif and Au25 with vertex-sharedbi-icosahedral motif.
2. Protection of Gold Clusters by Terminal Alkynes [3–5]Gold clusters protected by terminal alkynes, 1-octyne (OC-H), phenyl acetylene (PA-H) and9-ethynyl-phenanthrene (EPT-H), were prepared by the ligand exchange of the small (diameter<2nm) Au:PVP clusters. Vibrational spectroscopy revealed that the terminal hydrogen is lost during
the ligand exchange. A series of precisely-defined gold clusters, Au34(PA)16, Au54(PA)26,
Au30(EPT)13, Au35(EPT)18, and Au41-43(EPT)21-23, were synthesized and characterized in detail toobtain further insight into the interfacial structures. An upright configuration of the alkynes on Auclusters was suggested from the Au to alkyne ratios and photoluminescence from the excimer ofthe EPT ligands. EXAFS analysis implied that alkynyl carbon is bound to bridged or hollow sites on
the Au cluster surface.
Reference(s)[1] J. Nishigaki, R. Tsunoyama, H. Tsunoyama, N. Ichikuni, S. Yamazoe, Y. Negishi, M. Itoh, T.
Matsuo, K. Tamao, and T. Tsukuda, J. Am. Chem. Soc. 134 (2012) 14295.
[2] J. Nishigaki, S. Yamazoe, S. Kohara, A. Fujiwara, W. Kurashige, Y. Negishi, and T. Tsukuda,
Chem. Commun. 50 (2014) 839.
[3] P. Maity, H. Tsunoyama, M. Yamauchi, S. Xie, and T. Tsukuda, J. Am. Chem. Soc. 133(2011) 20123.
[4] P. Maity, T. Wakabayashi, N. Ichikuni, H. Tsunoyama, S. Xie, M. Yamauchi, and T. Tsukuda,
Chem. Commun. 48 (2012) 6085.
[5] P. Maity, S. Takano, S. Yamazoe, T. Wakabayashi, and T. Tsukuda, J. Am. Chem. Soc. 135(2013) 9450.

Structure and thermodynamics

A49

Isolation and properties of chiral Pd2Au36(SR)24 cluster
Noelia Barrabés,1 Bei Zhang,1 Houhua Li,2 Kaziz Sameh,3 Dawid Wodka,1 Clément Mazet,2 Jordi
Llorca4 and Thomas Bürgi1

3

1

Depart. of Physical Chemistry, University of Geneva, Geneva, Switzerland

2

Depart. of Organic Chemistry, University of Geneva, Geneva, Switzerland

Depart. of Industrial Engineering, Superior National School of engineers of Tunis, Tunis, Tunisia
4

Institute of Energy Technologies and Centre for Research in Nano Engineering, Technical
University of Catalonia, Barcelona, Spain

Doping of thiolated gold nanoclusters (Aun(SR)m) with metals such as Pd or Pt leads to the stability
and properties enhancement of Aun(SR)m clusters [1]. One of the most promising property of someof Aux(SR)n clusters is their intrinsic chirality even though the stabilizing ligand is achiral. However,up to now not much attention has been paid to the chirality of doped thiolate-protected gold
nanoclusters. Following a reported synthesis protocol [2], PdxAun-x(SR)24 nanoclusters have beensynthesized and separated by chiral HPLC chromatography leading to the isolation of the twoenantiomeric forms of Pd2Au36(SR)24, which show chiroptical signal by circular dichroism (CD)
spectroscopy.

Figure 1. Isolation and characterization of enantiopure Pd2Au36(SR)24
The ability to separate and store enantiomers of Pd doped clusters at room temperature enables
us to study their racemization by CD and their structure by XAFS, XPS and HRTEM. It revealed
the possibility of Pd doping at the surface of the thiolated gold cluster. Furthermore, Pd doping
substantially affects the flexibility of the Au(Pd) – S interface.
References[1] R.Jin and K.Nobusada, Nano Research. 7 (2014) 285[2] Y.Negishi,K.Igarashi, K.Munakata, W.Ohgake and K.Nobusada,Chem.Commun.48(2012) 660

Structure and thermodynamics

A50

Alternate shell structure in Fe-Co nanoparticles
Bheema Lingam Chittari1 and Vijay Kumar,1,2
1

Dr. Vijay Kumar Foundation(VKF), 1969 Sector 4, Gurgaon 122001, Haryana, India

2

Center for Informatics, School of Natural Sciences, Shiv Nadar University, Chithera, Gautam
Budh Nagar - 203207, U.P., India

FeCo alloys have received much attention because of their high permeability and saturation
magnetization in magnetic applications. Nanoalloys of Fe-Co are of interest as the magnetic
moments in nanoparticles are generally enhanced as it is the case for pure Fe clusters andassemblies of such nanoparticles are attractive for developing improved magnets. It is important tounderstand the atomic distributions in such nanoparticles as the magnetic behavior could besensitive to the distribution of atoms. We have explored from ab initio calculations the atomic
structure and alloying behavior in small nanoparticles of Fe-Co alloys by considering 55-atomMackay icosahedron of Fe-Co in which a 13-atom icosahedron is covered by 42 atoms. This has
20 triangular faces, 12 vertices and 30 atoms on the edges. We optimized different distributions ofFe and Co atoms and find that the optimized structures remain icosahedral and are ferromagnetic.
Among all the distributions we studied, the one with alternate shells of Co-Fe12-Co42 has thelowest energy with 4.5 eV/atom binding energy and 107 µB magnetic moments. In the case when
Fe atoms form the complete core (Fe13) and Co atoms form a complete shell i.e Fe13Co42
core-shell structure, we find that the energy is 0.43 eV higher and the magnetic moments increase
to 108 µB. Our results suggest that Fe atoms are preferred in the core and Co on the surface andthis is in agreement with the notion that the element with lower surface energy tend be on thesurface. In the lowest energy alternate shell structure the magnetic moment on each Fe atom is
2.4 µB, the central Co atom has 0.9 µB whereas each of 30 edge Co atoms has 1.7 µB and the 12
vertex atoms have 1.9 µB magnetic moments. We shall further discus the charge transfer andelectronic structure in these nanoalloys.
This work has been supported by the Asian Office of Aerospace Research and Development(AOARD)[1] B.L. Chittari and V. Kumar, to be published.

A51

Structure and thermodynamics

Bond Length Analysis of Au Nanoparticles Synthesized in Ionic Liquids
Yoshikiyo Hatakeyama,1 Kiyotaka Asakura,2 Ken Judai,1 and Keiko Nishikawa3
1

College of Humanities and Sciences, Nihon University, Tokyo, Japan
2

3

Catalysis Research Center, Hokkaido University, Hokkaido, Japan

Graduate School of Advanced Integration Science, Chiba University, Chiba, JapanAu nanoparticles (AuNPs) of varied sizes were

5

[C2mim]BF4[C4mim]PF6

synthesized in ionic liquids using sputter deposition
technique. As these AuNPs are dispersed freely inareoccasionallycallednaked-AuNPs.

To

characterize the structure of AuNPs, the values ofpeak positions were extracted as the size of
maximum abundance in AuNPs in each ionic liquidfrom size distribution curve obtained by small-angle

4

Diameter / nm

each ionic liquid without any stabilizing agents, they

3
2

1

X-ray scattering (SAXS). Figure 1 shows the size of
maximum abundance in AuNPs synthesized in20

1-ethyl-3-methyl

Preparation temperature / °C

imidazolium

tetrafluoroborate([C2mim]BF4) and 1-butyl-3-methyl imidazolium
hexafluorophosphate ([C4mim]PF6). Their sizes
were controlled by the types of ionic liquid[1] and

30

40

50

60

70

80

Figure 1. The size of maximum abundancein AuNPs in two ionic liquids.

the temperatures[2] during sputter deposition. To elucidate the Au-Au bond length of AuNPs in
relation to the particle size, X-ray absorption fine structures (XAFS) at Au L3-edge were measured.
From the analyses of XAFS, it was revealed that the bond lengths of Au-Au for AuNPs with thesize of about 1nm are 2.76–2.81 Å in contrast to 2.88 Å for bulk Au. Comparing our present resultsby SAXS and XAFS with previously-reported theoretical studies, we come to the conclusion thatthe surfaced Au atoms of the naked-AuNPs in ionic liquids have shorter bond length compared toinner atoms.
Acknowledgement
XAFS experiments were performed under the approval of the Photon Factory Program Advisory
Committee (Proposal No. 2007G518 and 2009G090). The present study was supported by aGrand-in-Aid for Scientific Research (No. 17073002 for K. N.) on Priority Area “Science on Ionic
Liquids” from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
References[1] Y. Hatakeyama, M. Okamoto, T. Torimoto, S. Kuwabata, and K. Nishikawa, J. Phys. Chem. C
113 (2009) 3917.
[2] Y. Hatakeyama, S. Takahashi, and K. Nishikawa, J. Phys. Chem. C 114 (2010) 11098.

Structure and thermodynamics

withdraw

A52

A53

Structure and thermodynamics

Generation of a liquid droplet in a vacuum
Kota Ando, Masashi Arakawa, and Akira Terasaki
Department of Chemistry, Kyushu University, Fukuoka, Japan
Liquids in a vacuum provide opportunities to apply gas-phase experimental techniques such as
mass spectrometry to chemical species in condensed phases. For example, biologicalmolecules are to be introduced in a manner closer to a native environment, i.e., in an aqueous
solution, which can be analyzed by mass spectrometry to extract structural information aboutsolvation. In turn, materials produced in the gas phase, such as metal clusters, are to be injected
in a liquid for performing wet chemistry. These ideas motivate us to develop a method togenerate a liquid droplet in a vacuum.
A schematic of the experimental apparatus is shown in Figure 1. A droplet with a diameter of
50−100 μm was generated on demand by a piezo-driven droplet nozzle, which was inserted into a
vacuum chamber. The droplet was illuminated by a pulsed strobe LED and was monitored byusing a camera for characterization. The liquid-sample reservoir was evacuated simultaneouslywith the chamber to avoid a spontaneous flow of the sample liquid into the chamber through thenozzle. The pressure inside the chamber was reduced down to 17 Pa using a rotary pump with
1.6 Ls−1 pumping speed.
In the present experiment, pure water and ethylene glycol were examined. The sample liquids
were deaerated in advance to avoid release of solute gases in a vacuum. In the case of purewater, the droplet generation was possible down to the 17 Pa. However, when the vacuum was
below the vapor pressure of water (2.3 kPa at 293 K), the droplet generation was not persistent
due to occasional boiling in the nozzle. In this respect, ethylene glycol was easier to handle,
enabling droplet formation regularly at 17 Pa, because its vapor pressure is much lower.
Liquid-to-solid phase transition in a vacuum was examined by illuminating the droplet with linearlypolarized light; scattered light should be depolarized, when a droplet is frozen. However, it was
found that a pure water droplet is not frozen even at 8.2 ms after generation at 21 Pa. The
survival of the liquid phase was further supported by thermodynamic simulation of droplet
temperature as a function of time. Figure 2 shows a cooling rate calculated for a water droplet
with 74-μm in diameter at 0 Pa. The temperature was predicted to be 240 K at 8.2 ms aftergeneration. This result implies that evaporative cooling down to 240 K is too fast for the water
droplet to be frozen. This is consistent with a previous report on homogeneous nucleation rates
in a nitrogen atmosphere showing a time constant of more than tens of second at 240 K [1].

Figure 1. Experimental apparatus

Figure 2. A cooling rate calculated for awater droplet with 74-μm in diameter at 0 Pa

[1] P Stöckel, I. M. Weidinger, H. Baumgärtel, and T. Leisner, J. Phys. Chem. A 109 (2005) 2540

Structure and thermodynamics

A54

Vibrational properties of metal nanoparticles: From structural dependence tointrinsic damping
Huziel E. Sauceda,1 Israel Acuña-Galván,2,3 and Ignacio L. Garzón1
1

Instituto de Física, Universidad Nacional Autónoma de México, Apartado Postal 20-364, 01000
México, D.F., Mexico
2

Centro Universitario UAEM Zumpango, Estado de México, C.P. 55600, Mexico
3

Escuela Superior de Tizayuca, UAEH, Hidalgo, C.P. 43800, Mexico

The experimental and theoretical study of vibrations of metal nanoparticles has become a fruitfulresearch field because of the lack of answers to fundamental questions as well as the potential
applications in Nanotechnology. Here, we report a detailed analysis on the morphologicaldependence of the vibrational density of states (VDOS) for crystalline (FCC) as well as
icosahedral and decahedral silver and gold nanoparticles (NP). Gold nanorods (GNR) of similar
size are also studied. On the other hand, a careful study of the intrinsic damping of the launchedbreathing mode (BM) on a gold NP is presented. The interactions between metal atoms weremodeled by the n-body Gupta potential. Using the well-known fact that the VDOS strongly
depends on the morphology of the NP[1,2] and recent experimental measurements of the VDOS
for Ag and Au NP[3,4], we have deduced the crystalline structure of the NP from the experiment by
a direct comparison of the VDOS (see Figure). In the study of the launched BM, we obtain asimple linear dependence of the damping time with temperature, tD=-aT+b, and consequently, thequality factor also depends in the same way. For applications of metal NP as a nanoresonators,
this is a very important result because it describes the behavior of the system's quality factor underchanges of temperature.

References[1] H.E. Sauceda, D. Mongin, P. Maioli, A. Crut, M. Pellarin, N. Del Fatti, F. Vallée and I.L. Garzón,
J. Phys. Chem. C 116 (2012) 25147.
[2] H.E. Sauceda, F. Salazar, L.A. Pérez and I.L. Garzón, J. Phys. Chem. C 117 (2013) 25160.
[3] M. Bayle, P. Benzo, N. Combe, C. Gatel, C. Bonafos, G. Benassayag, R. Carles, Phys. Rev. B
89 (2014) 195402.
[4] M. Bayle, N. Combe, N. Sangeetha, G. Viau, R. Carles, Nanoscale (2014), accepted.

A55

Structure and thermodynamics

An incorporation of the concept of a bifurcation pathway toglobal reaction route mapping analyses: An application to Au5 cluster
Tetsuya Taketsugu,1,2 Yu Harabuchi,1 Yuriko Ono,1 and Satoshi Maeda1,2
1
2

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, JapanFor a given polyatomic system, the global reaction route mapping (GRRM) analyses can give a
global map of reaction pathways which connect all possible minima via the correspondingtransition states (TSs) through the respective intrinsic reaction coordinates (IRCs) on the potential
energy surface (PES) [1]. The IRC is determined definitely as a steepest descent pathway inmass-weighted coordinates, starting from TS to reactant and product minima, for each elementary
reaction. Sometimes the IRC accompanies a valley-ridge inflection (VRI) point, which causes abifurcation of the valley paths. Fig. 1
illustrates two different cases of VRI
occurrences: (a) non-totally symmetric VRI
and (b) totally symmetric VRI. As shown in
Fig. 1, the IRC itself cannot bifurcate at VRI
points because a direction of the IRC isdefined mathematically as the negative
energy gradient. Therefore, in a global mapof reaction pathways obtained by GRRM
analyses,thebifurcationofreaction

pathways are not taken into account.

(a) non-totally symmetric(b) totally symmetricFig. 1. Schematic illustrations of VRI occurrences

The bifurcation of reaction pathways has been studied in many aspects [2-6], but all previous
studies focused on the specific reaction pathway of the specific reaction. In the present study, we
first applied the GRRM analyses to Au5 cluster, as an example, by DFT(PBEPBE)/lanL2DZ
calculations. It is shown that Au5 cluster has five minima and 14 transition states, which areconnected via IRCs. Then, we carried out normal mode analyses at chosen points along therespective IRCs, and calculated vibrational frequencies of all transverse modes from the projected
Hessians. As the results, the VRI points are found along four different IRCs. These VRI points are
successfully related to one of product minima which are not directly connected by the IRC. The
detailed discussions will be give in the presentation.
References[1] S. Maeda, K. Ohno, and K. Morokuma, Phys. Chem. Chem. Phys., 15 (2013) 3683.
[2] T. Taketsugu and T. Hirano, J. Chem. Phys., 99 (1993) 9806.
[3] T. Taketsugu, N. Tajima, and K. Hirao, J. Chem. Phys., 105 (1996) 1933.
[4] T. Yanai, T. Taketsugu, and K. Hirao, J. Chem. Phys., 107 (1997) 1137.
[5] Y. Harabuchi and T. Taketsugu, Theo. Chem. Acc., 130 (2011) 305.
[6] Y. Harabuchi, A. Nakayama, and T. Taketsugu, Comp. Theo. Chem., 1000 (2012) 70.

A56

Structure and thermodynamics

Stability and morphology ofplatinum cluster supported on silicon substrate in heating cycles
Nobuyuki Fukui,1 and Hisato Yasumatsu,21
2East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa, Japan

Cluster Research Laboratory, Toyota Technological Institute, Ichikawa, Japan

Size selected clusters supported on a substrate are model systems appropriate for studying
functional subnano-materials due to the advantage to design the surface structure precisely aswell as their behaviors far different from the corresponding bulk and even nano-particles.
We have succeeded to construct monatomic –layered uni-size Pt cluster disks on a Si(111)- 7x7
surface stably at 300 K, which induce two-dimensional charge polarization[1,2]. Considering
importance for their advanced application to catalysis, we investigated the stability andmorphology of the cluster disks in heating cycles under a UHV condition by means of scanningtunneling microscopy (STM) [3].
It was found by statistical analysis of the STM images that the diameter and height of the cluster
disk remain unchanged after heating at 673 K (see Figure1). Therefore, it is reasonable that thecluster disk is stable in heating at 673 K. Considering the diffusion of Si atoms in Pt/Si binary
systems below 600K, the higher thermal stability of the Pt cluster disk on the Si(111)-7x7 surface
is likely due to strong Pt-Pt interaction in the disk, which prevents the diffusion of the Si and Pt
atoms into the Pt cluster disks and the silicon substrate, respectively.
However, the height of the cluster disk tends toincrease with the heating temperature above 673 K. It
is also reasonable that Si atoms of the substratediffuse into the cluster disk.
When the samples are heated at 900 K, the number
density of the cluster disk containing Si atoms isincreased dramatically. It seems that the one or few
Pt atoms in the cluster disk also start to diffuse on thesubstrate surface in addition to diffusion of Si atoms
into the cluster disk.
After heating at 1000 K, bigger island appear on asingle-crystal Si surface as a result of the diffusion of
the Pt atoms into bulk.

Figure 1: Temperature dependence ofReference(s)[1] H.Yasumatsu et.al, J. Chem. Phys.,123(2005) 12470[2] H.Yasumatsu et.al, Chem. Phys. Lett.,487(2010) 279[3] N Fukui and H. Yasumatsu, Eur.Phys.J.D. 67 (2013)81/1-4

Apparent height of Pt30 disk
at two cluster density

A57

Structure and thermodynamics

Synthesis of a novel [core+exo]-type heptanuclear gold cluster
Mingzhe Zhang,1 Yukatsu Shichibu,1,2 and Katsuaki Konishi1,21Graduate School of Environmental Science, Hokkaido University, Sapporo, 060-0810, Japan

2

Faculty of Environmental Earth Science, Hokkaido University, Sapporo, 060-0810, Japan

Subnanometer-sized clusters with nuclearity of around 10 have recently attracted much interest,
not only due to the fundamental aspects of their unique nuclearity- and structure-dependent
optical and electronic properties but also to their potential in the development of novel
nanomaterials and catalysts. Previously we have shown that [Au6(dppp)4]2+ (1), [Au8(dppp)4Cl2]2+and [Au11(dppe)6]3+ (dppp = Ph2P(CH2)3PPh2, dppe = Ph2P(CH2)2PPh2) adopt unusual [core+two]
geometries having two exo gold atoms attached to the polyhedral cores, and demonstrated theirgeometry-dependent optical properties and electronic structures [1-3]. Herein, we report the firstexample of trivalent heptanuclear gold cluster [Au7(dppp)4]3+ (2) with a [core+one] structure.
2 synthesized by the growth reaction of 1 in
the presence of silver ion (Fig.1).
Ag +Single-crystal X-ray structural analysis of 2
revealed that it had an edge-sharing
bi-tetrahedral core with one edge-bridging gold [Au (dppp) ]2+ (1)[Au 7 (dppp)4 ]3+ (2)64
atom at one side of the exo positions. This
structure can be viewed as a derivative of theFig.1 Skeletal structures of cluster 1 and 2.
precursor 1, in which one of the exo gold
atoms of 1 accommodate an extra Au(I). Butinterestingly, the growth reaction of 1 to form 2
didn’t proceed by using gold ion. Like other[core+exo] type gold clusters, UV-vis
absorption spectrum of 2 showed an isolated
absorption band, which was assigned to
HOMO-LUMO electronic transition. So these[core+exo] clusters can be considered to showcommon absorption properties. In addition, 2also showed an evident photoluminescenceband at 642 nm (Fig.2).

References[1] Y. Kamei, Y. Shichibu, and K. Konishi,

Fig.2 Absorption, emission (λex = 555 nm)
and excitation (λem = 642 nm) spectra of 2.

Angew. Chem. Int. Ed. 50 (2011) 7442.
[2] Y. Shichibu, Y. Kamei, and K. Konishi, Chem. Commun. 48 (2012) 7559.
[3] Y. Shichibu, and K. Konishi, Inorg. Chem. 52 (2013) 6570.

Structure and thermodynamics

A58

Exploration on Magic Binary Nanoclusters Consisting of Silicon-Transition
Metal Atoms by Reaction with Molecular Oxygen
Yoshito Sugawara,1 Tomomi Nagase,1 Hironori Tsunoyama,1,2 and Atsushi Nakajima1,2
12

Department of Chemistry, Keio University, Japan
Nakajima Designer Nanocluster Assembly Project, JST-ERATO, Japan

Nanoclusters (NCs) with early transition metal (M=Groups 3–5 elements) encapsulated in a Si16
cage have been received intensive research interest1-3 because of their size-specific stability
originating from concerted electronic and geometric shell closing. Replacement of interior metal
atom with other elements is one of the potential method to open up wide functionality ofmetal-silicon binary NCs. In this study, we investigated magic numbers in binary NCs consisting ofsilicon (Si) and late transition metal (M=Pd, Ni, and Rh) by utilizing a magnetron type NC ion
source combined with reaction with molecular oxygen (O2). Since the O2 exposure causes etching
reactions of NC ions, the reaction enhances the relative population of magic NC ions with metal
encapsulation, such as M@Si16+/–, in M-Si binary NCs. Magic numbers in the M-Si NCs (M=Pd, Ni,
and Rh) were investigated by the etching reaction and their origin was discussed based on themetal-element dependence.
Positive and negative ions of binary NCs were generated by a magnetron type NC source4 andsize distributions were monitored by a quadrupole mass spectrometer. Magic number behaviors
were investigated by the comparison of mass spectra with or without the reaction with O2; thepristine NCs were reacted with O2 at the downstream of the NC source, which was introduced as
effusive beam perpendicular to the NC beam.
Figure 1 shows representative mass spectra of Pd-Si binary NC cations with or without reaction of
O2. Without reaction of O2, a series of Sin+, PdSin+, and Pd2Sin+ cations were observed (Fig. 1 top).
After the reaction (Fig. 1 bottom), the intensities of PdSi10+ and PdSi13+ become relatively
prominent as compared with the other PdSin+ ions. The similar magic number behavior was also
observed in Ni-Si binary NC cations, where both Ni and Pd belong to group 10 in the periodic table.
However, the magic number behavior was not observed apparently at the same sizes in Rh (group9)-Si binary cations after reacting with O2, although the intensity of RhSi5+ was relatively strong.
Therefore, the common magic numbers of MSi10+ and MSi13+ observed for M=Pd and Ni were
attributable to isoelectronic characteristics of the binary NCs, because the atomic radii of Ni and
Pd are different, while those of Rh and Pd are almost similar.

Figure 1. Mass spectra of Pd-Si NC cations.
(source conditions; Ar 122 sccm, He 200 sccm, Power 50 W)
References[1] K. Koyasu et al., J. Am. Chem. Soc. 127 (2005) 4998. [2] J. T. Lau et al., J. Chem. Phys. 134(2011) 041102. [3] P. Claes et al., Phys. Rev. Lett. 107 (2011) 173401. [4] H. Tsunoyama et al.,Chem. Lett. 42 (2013) 857.

A59

Structure and thermodynamics

Preparation and redispersible solidification of monodisperse CdSe
nanoparticles capped with cysteine in water
Yasuto Noda, Isao Sawakami, Takuya Kurihara, and K. Takegoshi
Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto, Japan
In this presentation we report on the preparation of monodisperse CdSe nanoparticles (NPs)capped with cysteine in water and the redispersible solidification without destruction. Using
solid-state NMR, we studied the details of the interaction providing the reversibility between the
capping cysteine and the CdSe NPs.
The synthetic procedure of CdSe NPs is as follows: Se and Cd precursor solutions were preparedwith dissolving elemental Se in Na2SO3 aq. and Cd(OH)2 in cysteine aq. with the cysteine/Cd ratio
of 4, respectively. Then the solutions were mixed in room temperature so as to be the Cd/Se ratioof 2 under pH of ca. 13 adjusted with NaOH aq. As shown Fig. 1(a), the solution showed the sharp
absorption peak with the FWHM of 13 nm, which indicates monodisperse CdSe NPs were grown.
The CdSe NPs powder was obtained by adding acetone as an antisolvent to the solution after pH
adjustment of 11 followed by drying with a vacuum pump after centrifugation. The absorption
spectrum after redispersion of the obtained powder into water resembled one before thesolidification closely as shown Fig. 1(b).
Moreover, the powder XRD pattern showed
any clear peaks indicating coalescence of
CdSe NPs. Thus the CdSe NPs could be
solidified without destruction.
In order to investigate the stability of CdSe
NPs, solid-state 13C NMR was performed.
The {1H}-13C cross-polarization magic-angle
spinning NMR spectrum showed the thiol andamino groups bound to CdSe NPs, while thecarbonyl group did not. Moreover, any freeFigure 1 Absorption spectra of CdSe NPs aq.

cysteines were observed. Thus, the CdSe(a) just after preparation and (b) redispersed

NPs should

after solidification.

becovered withcysteinemonolayers.
This work is supported by JSPS KAKENHI Grant Number 25888009.

A60

Structure and thermodynamics

Low temperature XAFS study of thiolate-protected Au clusters
Seiji Yamazoe,1,2 Shinjiro Takano,1 Wataru Kurashige,3 Yuichi Negishi,3 and Tatsuya Tsukuda1,2
1

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
2

3

ESICB, Kyoto University, Kyoto, Japan

Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Tokyo,
Japan

X-ray absorption spectroscopy (XAFS) is a powerful tool to

1 Au–S

probe the local structure of a specific element. Recently, we

FT of k3 χ (k)determined by Pd K-edge EXAFS that a Pd dopant atom in
Au24Pd1(SC12H25)18 is located at the center of icosahedral Au
core [1]. However, EXAFS data of thiolate-protected Auclusters measured at RT underestimate the coordination
numbers (CNs) of Au-Au bonds determined by the single

300 K
Au–Au

crystal XRD, which is probably due to thermal fluctuation of

8K

Au atoms in the small clusters. We report herein that detailed
structure information can be obtained from EXAFS data

0

1

2

3

4

5

6

recorded in wide k region at <10 K. We also demonstrate theR/Åsoftening of the Au-Au bond by the analysis of theFig. 1 Au L3-edge FT-EXAFS spectraof Au25(SC2H5Ph)18 at 300 K and 8 K

temperature dependence.

The XAFS spectra of Au25(SC2H5Ph)18, Au38(SC2H5Ph)24, and Au144(SC2H5Ph)60 at Au L3-edge
were recorded at BL01B1 beam line in SPring-8. Fig. 1 shows the Au L3-edge Fourier transformed(FT) EXAFS spectra of Au25(SC12H25)18 measured at 300 and 8 K. The peaks assigned to theAu–Au bonds are clearly discernible at 8 K. This is due to the suppression of thermal fluctuation of
Au atoms. Curve fitting analysis for Au25 cluster was performed assuming one Au–S bond and two
types of Au–Au bonds (Table 1). The bond lengths and CNs of the Au–S and Au–Au bonds
obtained from the curve fitting analysis agreed well with those determined from the single crystal
X-ray

analysis[2].

results

wereobtained

Au38(SC2H4Ph)18

Similarfor

Table 1 Result of curve fitting analysis and structural parameters obtained
from X-ray single crystal analysis of Au25(SC2H5Ph)18

andSampleAu144(SC2H4Ph)60. Finally, theEinsteintemperature

Au25(SC2H4Ph)18
at 8 K(θE),

which is related to the bondstiffness, of each bond wasestimatedfromtemperature-dependent
Debye-Waller factors.

Au25(SC2H4Ph)18
Single crystal [2]

the
a

Atom

CNa

S
Au1
Au2
S
Au1
Au2

1.6(2)
1.4(8)
1.9(1.1)
1.4
1.4
1.9
b

r (Å)b

DWc

2.321(4) 0.0049(12)2.759(17) 0.0034(33)2.906(29) 0.0072(118)
2.33
2.784
2.948
c

R (%)d12.0

d

CN: coordination number, r: bond length, DW: Debye-Waller factor, R:
R factor

References[1] Y. Negishi et al., J. Phys. Chem. Lett. 4 (2013) 3579.
[2] M. A. MacDonald et al., J. Phys. Chem. C 115 (2011) 15282.

Structure and thermodynamics

A61

Ionic cluster formation using an ion drift-tube with selected-ion injection- Measurement of thermodynamic quantities for H3O+ Hydrate
Yoichi Nakai1, Hiroshi Hidaka2, Naoki Watanabe2 and Takao M. Kojima3
1

RIKEN Nishina Center for Accelerator-Based Science, Wako, Saitama 351-1098, Japan
2

Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan
3

Atomic Physics Laboratory, RIKEN, Wako, Saitama 351-0198, JapanFor the decades, ion-induced nucleation has attracted attentions as one of important processes
for gas-phase nucleation because a free-energy barrier for growth of particles decreases byelectrostatic attractive forces originating from polarization of atoms/molecules, e.g., as shown forthe classical liquid drop model. In particular, ionic cluster formation, an early stage of theion-induced nucleation, is a significant research subject since it governs the subsequent stages.
Thus far, the ionic cluster formation has been widely investigated from various research points ofview. In many of experimental studies, however, the formation processes were triggered in areactant gas including parent molecules of core ions by discharge, a pulsed electron beam,
radiation sources, and so on. In such a situation, various ionic species can be produced together
with desired ionic core ions. Thus, initial ionic reactions were not well defined, generally. In order
to eliminate reactions by undesired ions, we developed an experimental apparatus, an ion
drift-tube with selected-ion injection [1-3], where only specific parent ions are injected to a reaction
cell.
We measured H3O+ hydrate, i.e., H3O+(H2O)n cluster ions, produced in a mixed gas of helium andwater in the temperature range from 224 to 403K and estimated the Gibbs free-energy changes
for the stepwise association of a water molecule, H3O+(H2O)n-1 + H2O -> H3O+(H2O)n. The
thermodynamic quantities, the enthalpy changes and the entropy changes, were also estimated.
The obtained values are reasonably consistent with those of the preceding investigations [4,5]. In
addition, we also show the experimental results of NO+(H2O)n formation briefly, which we recently
measured [6].
Reference(s)[1] H. Böhringer and F. Arnold, Int. J. Mass Spectrom. and Ion Phys. 49 (1983) 61.
[2] T. M. Kojima et al., Z. Phys. D: At., Mol. Clusters 22 (1962) 645.
[3] H. Tanuma et al., Rev. Sci. Instrum. 71 (2000) 2019.
[4] NIST Chemistry WebBook, http://webbook.nist.gov/chemistry/.
[5] K. D. Froyd and E. R. Lovejoy, J. Phys. Chem. A 107 (2003) 9800.
[6] H. Hidaka et al., poster presentation in this symposium.

Structure and thermodynamics

A62

Nanoparticle formation by interaction between laser ablated plume andshock waves
Eri Ueno1, Naoaki Fukuda2, Hiroshi Fukuoka3, Minoru Yaga4, Ikurou Umezu5
Min Han6 and Toshio Takiya1
1
2
3
4

Hitachi Zosen Corporation, Osaka, Japan

Office of Society-Academia Collaboration for Innovation, Kyoto University, Kyoto, Japan

Department of Mechanical Engineering, Nara National College of Technology, Nara, Japan

Department of Mechanical Systems Engineering, University of the Ryukyus, Okinawa, Japan
5
6

Department of Physics, Konan University, Kobe, Japan

Department of Materials Science and Engineering, Nanjing University, Nanjing, China

Pulsed laser ablation in background gas is one of techniques to produce nanoparticles with a
precisely specified size. Production of nanoparticles with the desired size is possible because theconditions for evaporated mass and ambient gas pressure can be independently controlled [1].
Although observation of the laser ablation processes by spectroscopic methods gives aninformation on the plume expansion dynamics, effect of shock wave is not clear [2]. Shock waves
generated in the early stage of the laser ablation process reflect and diffract at the substrate.
These make the clarification of the nanoparticle formation process difficult. Hitherto, little papers
have discussed effect of these shock waves on the plume dynamics and nanoparticle formation
processes[3][4]. We investigated the interaction between laser ablated plumes and shock waves
using one- and/or two-dimensional Eulerian fluid dynamics equations combined with a classicalnucleation model in supersaturated vapors. We found that the rate of nanoparticle formation
becomes higher when a plume locates between the target and substrate and reflected shock wave
passes through the plume. In that case, a sudden change in temperature could be generated near
the interference between the shock wave and the plume, followed by the formation of
nanoparticles in the narrow region.
References[1] N. G. Semaltianos, Crit. Rev. Solid State Mater. Sci., 35-2, (2010) 105. (Journals)[2] G.W.Yang, Prog. Mat. Sci., 52, (2007) 662-664. (Journals)[3] M.Han et al., Phys. Lett., A302, (2002)182. (Journals)[4] M. Yaga, T. Takiya and Y. Iwata: Shock waves, 14-5/6, (2005) 403. (Journals)

Structure and thermodynamics

A63

Structures of small silicon-doped gold cluster cations
Jun Miyawaki and Ko-ichi Sugawara
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan
Gold nano-clusters have been attracting much attention because of their catalytic properties andtheir size-dependency of geometries and reactivity has been investigated experimentally andtheoretically. Doping effect of foreign atom(s) on the structures and reactivity of gold clusters is
also interesting subject. Since photoelectron spectra of the silicon-doped gold cluster anions wereobserved by Wang and co-workers [1], a number of theoretical works have been reported in thisdecade on the structures of silicon-doped gold clusters, but they are mostly limited to the neutral
and anionic species. In the present study, structural evolutions of the silicon-doped gold cluster
cations, AunSim+, have been investigated for n=1-6 and m=1,2 using density functional theory
calculations.
Shorter bond length and larger dissociation energy of AuSi+ compared with Au2+ and Si2+ suggestthat Au-Si bond is stronger than Au-Au bond and Si-Si bond in their diatomic cations. Doping ofsilicon atom(s) in the pure gold cluster cations causes significant change on their structures. Mostof the structures of the lowest energy AunSim+ (n=1-6,m=1,2) isomers correspond to those of thecounterpart SimHn+, i.e., Au/H analogy found for the neutrals and anions by Wang’s group [1,2]holds for the cations as well. For n=1-4, the structures of AunSi+ are the same as thecorresponding SiHn+ cations. However, Au5Si+ has the penta-coordinated capped square prism
structure which is different from the experimentally observed SiH3+-H2 structure of SiH5+. Au6Si+ is
built based on Au5Si+ motif, which may be taken as beginning of the Aun-Si-Au structure reported
for the larger clusters. For AunSi2+, the most stable isomers have the same structures as Si2Hn+ in
n=2, 3, and 5. In case of n=4, second stable isomer has the same structure as Au4Si2 concluded
from PES experiment [2] although the most stable isomer has the different structure. Au6Si2+ has
the different structure from the experimentally confirmed D3d H3Si-SiH3+ structure.
References[1] B. Kiran, X. Li, H.-J. Zhai, L.-F. Cui, L.-S. Wang, Angew. Chem. Int. Ed. 43 (2004) 2125.
[2] X. Li, B. Kiran, L.-S. Wang, J. Phys. Chem. A 109 (2005) 4366.

A64

Structure and thermodynamics

Location of dopant M (M = Pd, Ag, Cu) within Au25-xMx(SR)18 studied by XAFS
Seiji Yamazoe,1,2 Wataru Kurashige,3 Katsuyuki Nobusada,2,4 Yuichi Negishi,3 andTatsuya Tsukuda1,2
1

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
2

3

ESICB, Kyoto University, Kyoto, Japan

Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Tokyo,
Japan

4

Department of Theoretical and Computational Molecular Science, Institute for Molecular Science,
Okazaki, JapanOne of the ubiquitous thiolate-protected Au clusters, Au25(SR)18,

AuC

has an icosahedral Au13 core surrounded by six -SR-(Au-SR)2oligomers (Fig. 1)[1]. Recently, bimetallic clusters Au25-xMx(SR)18(M = Pd[2], Ag[3], Cu[4]) have been successfully synthesized.
However, it has not yet been revealed which site is the dopant M
occupies among three sites; core-center (AuC), core-surface(AuS), or oligomer (AuO). In this work, the location of M within
Au25-xMx(SR)18 was studied by X-ray absorption spectroscopy(XAFS).
Bimetallic clusters Au24Pd1(SC12H25)18, Au25-xAgx(SC2H4Ph)18

S AuS

AuO
1

Fig. 1 Structure of Au25(SR)18.
The R groups are omitted forsimplicity.

(x=1–4), and Au25-xCux(SC2H4Ph)18 (n=1–3) were synthesizedaccording to the previously reported methods[2-4]. The XAFS
spectra at Pd K-, Ag K-, Cu K-, and Au L3-edges were recorded at
BL01B1 beam line in SPring-8. Structures of bimetallic clustermodels, MP, obtained by replacing AuP with M were optimized bydensity functional theory (DFT) using PBE0 functional. Then,
EXAFS oscillations of the optimized models were simulated by
FEFF8[5]. Fig. 2 shows the Pd K-edge EXAFS spectrum of
Au24Pd1(SC12H25)18 and the simulated EXAFS spectra of the PdC,
PdS, and PdO. The EXAFS oscillation pattern experimentallyobtained agrees well with that of PdC, which is the most stablestructure[6]. Similar analysis revealed that Ag dopants occupy

Fig. 2 Pd-K edge EXAFS spectraof Au24Pd1(SC12H25)18 obtainedby (a) experiment, (b) PdC, (c)PdS, and (d) PdO models.

core-surface sites in Au25-xAgx(SC2H4Ph)18 whereas Cu dopants are located at the oligomer sites
in Au25-xCux(SC2H4Ph)18.
References:[1] M.W. Heaven et al., J. Am. Chem. Soc., 130 (2008) 3754.
[2] Y. Negishi et al., Phys. Chem. Chem. Phys. 12 (2010) 6219.
[3] Y. Negishi et al., Chem. Commun. 46 (2010) 4713.
[4] Y. Negishi et al., J. Phys. Chem. Lett. 2 (2012) 2209.
[5] A. L. Ankudinov et al., Phys. Rev. B., 58 (1998) 7565.
[6] Y. Negishi et al., J. Phys. Chem. Lett., 4 (2013) 3579.

A65

Structure and thermodynamics

Space-Focusing of Spatially Spread Ionsin Time-of-Flight Mass Spectrometer
Shun Sarugaku, Ryohei Murakami, Masashi Arakawa, and Akira Terasaki
Department of Chemistry, Kyushu University, Fukuoka, Japan
A time-of-flight mass spectrometer (TOF-MS) is a powerful tool for rapid analysis over a wide
range of masses within tens of micro seconds. Focusing of ions is crucial in TOF-MS to achieve
high resolution. The standard technique is the Wiley-McLaren type, where spatial distribution ofions is compensated for by a double electric-field configuration, so-called space-focusing.
However, space-focusing does not work well when the spatial spread of ions is too large. Here
we demonstrate that the mass resolution is improved even for ions spread over the entire
accelerator region of TOF-MS by applying a non-linear electric potential to the accelerator.
We constructed TOF-MS illustrated in Fig.1. An ion beam was introduced coaxially to the flightpath.

The ions were extracted toward an ion

detector by applying pulsed voltages to electrodes
EL1 and EL2. All the electrodes had a 20-mm
diameter ion-inlet aperture. The aperture of EL2
was with a metal mesh for an ordinary linear
electric potential in the accelerator, whereas themesh was removed when applying a non-linear
potential.

Fig. 1. A schematic view of the present time-of-flightmass spectrometer.

Figure 2(a) shows a TOF mass spectrum of an ion
beam of Ag7+ from a continuous cluster-ion source,which filled the entire s-region of the TOF
accelerator. The mass resolution was very low
with meshes on all the electrodes. It was foundby ion-trajectory simulation that ions near the exitof the s-region at t = 0 μs have TOF shorter than
the rest of the ions.

The resolution was

improved by applying a non-linear potential sothat these ions are accelerated by less voltages+

Fig. 2. TOF mass spectra of Ag7 measured withmeshes on all the electrodes (a), and on
EL1 only (b). The peaks marked withasterisks are ringing noise.

and thus have longer TOF. Figure 2(b) shows a
TOF mass spectrum improved by this method.
The TOF-MS was further combined with a linear
ion trap. Ions were trapped for 50 ms, extracted
from the trap, and introduced coaxially to the flight
path, which produced a quasi- continuous ion
beam. We were able to separate isotopomers of
Ag3+ clearly as shown in Fig. 3.

+

Fig. 3. A TOF mass spectrum of Ag3 extracted
from a linear ion trap.

A66

Reactivity and catalysis

Understanding and designing nanoalloys for clean energy applications by firstprinciples calculations
Daojian Cheng*State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, P.R. China*E-mail: chengdj@mail.buct.edu.cn
With respect to the catalysts, alloy surfaces and nanoalloys have been employed to improve thecatalytic activity of oxygen reduction reaction (ORR), CO oxidation, and CO2 conversion. Here,first principles density functional theory (DFT) calculations have been used to study the oxygen
reduction reaction (ORR) activity of Pt-based alloy surfaces and nanoalloys,1,2 CO oxidation
activity of Au-Pd nanoalloys,3,4 and CO2 conversion activity of Cu-Ni nanoalloys.5,6 In addition,
new TiO2-based photocatalysts have been developed by DFT calculations.7-11
References:1)

Wenjie Xu, Daojian Cheng*, Mang Niu, Xiaohong Shao*, and Wenchuan Wang,
Modification of the adsorption properties of O and OH on Pt–Ni bimetallic surfaces by
subsurface alloying Electrochimica Acta 76, 440-445(2012)
2) Daojian Cheng*, Wenchuan Wang, Tailoring of Pd–Pt bimetallic clusters with high stability
for oxygen reduction reaction Nanoscale 4, 2408-2415 (2012)
3) Mingjiang Li and Daojian Cheng*, J. Phys. Chem. C 2013, 117, 18746−18751
4) Daojian Cheng*, Haoxiang Xu, Alessandro Fortunelli*, Journal of Catalysis 2014, 314, 47–
555) Yang Yang and Daojian Cheng*, Role of Composition and Geometric Relaxation in CO2
Binding to Cu-Ni Bimetallic Clusters J. Phys. Chem. C 2014, 118, 250-258
6) Daojian Cheng*, Fabio R. Negreiros, Edoardo Aprà and Alessandro Fortunelli*,
Computational approaches to the chemical conversion of carbon dioxide ChemSusChem,
2013, 6, 944 – 965
7) M. Niu, W. Xu, X. Shao*, Daojian Cheng*, Enhanced photoelectrochemical performance ofrutile TiO(2) by Sb-N donor-acceptor coincorporation from first principles calculations,Applied Physics Letters 99 (2011).
8) M. Niu, Daojian Cheng*, D. Cao*, Enhanced photoelectrochemical performance of anatase
TiO2 by metal-assisted S-O coupling for water splitting, International Journal of Hydrogen
Energy 38, 1251 (2013).
9) M. Niu, Daojian Cheng*, D. Cao*, Understanding Photoelectrochennical Properties of B-N
Codoped Anatase TiO2 for Solar Energy Conversion, Journal of Physical Chemistry C 117,
15911 (2013).
10) M. Niu, Daojian Cheng*, D. Cao*, Understanding the Mechanism of Photocatalysis
Enhancements in the Graphene-like Semiconductor Sheet/TiO2 Composites, Journal of
Physical Chemistry C 118, 5954 (2014).
11) M. Niu, Daojian Cheng*, D. Cao*, SiH/TiO2 and GeH/TiO2 Heterojunctions: Promising
TiO2-based Photocatalysts under Visible Light, Scientific reports 4, 4810 (2014).

Reactivity and catalysis

A67

Conformations of Biomolecular Ions Probed by Proton Transfer Reactions at
Various Temperature
Shinji Nonose, Minami Kawashima, and Hideo Isono
Graduate School of Nanobioscience, Yokohama City University, Japan
Investigations of gas-phase protonated biomolecules are motivated by the growing prevalence ofelectrospray ionization (ESI) mass spectrometry, which produce gas-phase biomolecular ions.
Access to biomolecules in the gas phase provides the opportunity to study them in isolated states.
The advantage of gas-phase studies is that ideas can be tested as finite molecular systems. In thepreset study, proton transfer from multiply-protonated protein and peptide ions to gaseous
molecules was studied in the gas phase. Absolute reaction rate constants for proton transfer were
determined from intensities of parent and product ions in the mass spectra. Temperaturedependence of reaction rate constants and branching fractions for proton transfer was measured.
An issue that is attracting considerable attention is vacuo conformations might resemble structural
evolution that originates in temperature change in the gas phase.
A home-made tandem mass spectrometer with ESI was used for measurements. Multiply-charged
protein and peptide ions were produced by ESI of a dilute solution in methanol-water mixture
including acetic acid. The charge-selected protein and peptide ions emerging from a quadrupole
mass spectrometer (QMASS) were admitted into a collision cell with octapole ion trap. The
collision cell was filled with He including gaseous molecules. Primary, secondary, and aromatic
amines were chosen as target molecules. Temperature dependence of reaction rate constants andbranching fractions for proton transfer from multiply-charged protein and peptide ions to the target
molecules was measured, by changing temperature of the collision cell. The parent and productions were mass-analyzed by a time-of-flight mass spectrometer equipped with reflectron.
Proton transfer from the protein and peptide ions to the target molecules was occurred bycollisions in the cell. Absolute reaction rate constants for proton transfer were estimated withintensity of ions in the mass spectra. In any protein and peptide ions, the reaction rate increased
rapidly with increase of charge states. By changing temperature of the collision cell in region from
280 to 470 K, temperature dependence of reaction rate constants and branching fractions for
proton transfer was measured. Dramatic change was observed for distribution of product ions andreaction rate constants. These results would correlate to conformation change of protein andpeptide ions with change of temperature, which originates in self-solvation to protons byhydrophilic residues in polypeptide chains, delocalization of charges with self-solvation, andCoulomb repulsion between charges.
References[1] S. Nonose, T. Okamura, K. Yamashita, A. Sudo, Chemical Physics, 419 (2013) 237–245.
[2] S. Nonose, K. Yamashita, A. Sudo, M. Kawashima, Chemical Physics, 423 (2013) 182–191.

A68

Reactivity and catalysis

Reactions of Copper Cluster Oxide Anions with Nitric Oxide:
Enhancement of Adsorption by Partial Oxidation
Shinichi Hirabayashi,1 and Masahiko Ichihashi2
1
2

East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa, Japan

Cluster Research Laboratory, Toyota Technological Institute, Ichikawa, Japan

Recently we have found that a carbon monoxide molecule is oxidized by copper oxide cluster
anions, and in this reaction the deformation of the clusters and the resulting change of theirelectronic structures facilitate the progress of the reaction [1]. Here, we show that a nitrogenmonoxide, NO, molecule can adsorb onto the copper oxide anions efficiently [2], and thisadsorption leads to the reduction of NO.
Reactivity measurements were performed by use of a tandem-type mass spectrometer. Copper
cluster ions were produced by the ion-sputtering of copper targets, and oxidized by oxygen
molecules. Then bare or oxidized copper cluster ions were mass-selected by a quadrupole massfilter (QMF), and allowed to pass through a reaction cell filled with NO gas. Product ions andunreacted parent cluster ions were mass-analyzed by the second QMF.
In the reactions of CunO2- with NO at the collision energyof 0.2 eV, the following products were observed,
CunO2- + NO  CunO2(NO)-,(1)

CunO2- + NO  Cun-1O2(NO)- + Cu.

(2)

The total reaction cross sections are shown in Fig. 1, andeven-sized clusters have relatively large cross sections in
n  8.

NO adsorption is often accompanied by therelease of a Cu atom from Cu8O2-, Cu10O2- and Cu12O2- as
indicated in reaction (2). On the other hand, Cun- havesignificantly small cross sections in comparison withCunO2-.

-

Fig.1: Reaction cross sections of Cun
and CunO2 .

Further, we measured the reaction crosssections of Cu8O4- and Cu8O6- for comparison, and foundthat only Cu8O2- has a large reaction cross section (seeFig. 2). In order to elucidate this specific reactivity, we
calculated the reaction diagram of CunOm- + NO by using
DFT, and this suggests that the energy of the transition
state between the molecular and the dissociative
adsorption of NO reduces remarkably by the partial
oxidation of the copper cluster anions.
References

Fig.2: Reaction cross sections of
Cu8Om .

[1] S. Hirabayashi, Y. Kawazoe, and M. Ichihashi, Eur. Phys. J. D 67 (2013) 35.
[2] S. Hirabayashi, and M. Ichihashi, J. Phys. Chem. A 118 (2014) 1761.

A69

Reactivity and catalysis

Vibrational Spectroscopy of Aluminum Oxide Cluster Anions: Structure andReactivity

Xiaowei Song,1,2 Matias R. Fagiani,1,2 Florian A. Bischoff,3 Wieland Schöllkopf,1 Sandy
Gewinner,1 Joachim Sauer3 and Knut R. Asmis1,2

1

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany.
2

3

Wilhelm-Ostwald-Institut, Universität Leipzig, Linnéstr. 2, 04103 Leipzig, Germany

Institut für Chemie, Humboldt-Universität Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany

Aluminum oxides serve as highly efficient heterogeneous catalysts and catalyst supports. In
particular, they are used for methane activation and promote various H/D exchange processes.[1]However, a molecular level understanding of the elementary reaction mechanisms and the natureof the involved active sites remains limited. Spectroscopic studies on size-selected gas phaseclusters [2,3] can aid in gaining insight into the concepts governing these processes. Here, we
use infrared photodissociation in combination with the intense and widely-tunable radiation fromthe IR free electron laser FHI-FEL [4] to study the structure and reactivity of aluminum oxide
cluster anions in the gas phase. The nominally electronic closed shell clusters (AlO2)(Al2O3)-x=0-3
as well as the open shell clusters AlOx=1-4 and Al2Ox=3-6 are probed. Structures are assigned
based on a comparison of the IRPD spectra of the H2-tagged cluster anions to simulated IR
spectra from electronic structure calculations. The terminal Al-O stretching modes involving
singly-coordinated oxygen atoms are found in-between 950 and 1200 cm-1. Al-O stretchingmodes involving doublyand triply-coordinated O-atoms lie lower in energy (600-950 cm-1) and OAl-O bending modes are found below 600 cm-1. For some of the open-shell cluster anions
reactions with the H2-messenger molecules are observed. The underlying reaction mechanism isstudied in more detail in our ion trap setup, i.e., rate constants are determined from concentration
profiles measured as a function of the reaction time and the ion trap temperature. Preliminary
results from the reactivity studies of the clusters anions with water are also shown.

References[1] Wang Z., Wu X., Zhao Y., Ma J., Ding X., He S.,Chem. Eur. J. 17, 3449-3457 (2011).
[2] G. Santambrogio, E. Janssens, S. Li, T. Siebert, G. Meijer, K.R. Asmis, Jens Döbler, M. Sierka,
J. Sauer, J. Am. Chem. Soc. 130, 15143-15149 (2008).
[3] Sierka, J. Döbler, J. Sauer, G. Santambrogio, M. Brümmer, L. Wöste, E. Jannsens, G. Meijer,
K.R. Asmis, Angew. Chem. Int. Ed. 46, 3372-5 (2007).
[4] Schöllkopf, W., Gewinner, S., Erlebach, W., Heyne, G., Junkes, H., Liedke, A., et al. (2013). In
Proceedings of FEL 2013, New York, NY, USA (pp. 657-660).

A70

Reactivity and catalysis

Homogeneous deposition of size-selected clusters
using Lissajous scanning method
Atsushi Beniya1, Noritake Isomura1, Hirohito Hirata2 and Yoshihide Watanabe1
1

Toyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan ,2
Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193, Japan

Size-selected atomic clusters on surfaces are a subject of considerable interest because of their
distinctive size-dependent catalytic properties. Conventionally, the cluster deposited surfaces
were prepared by irradiating the sample surface to cluster ion beam. In order to investigate
deposited isolated clusters, it is crucial to define the cluster coverage. However, due to intensity
distribution of the ion beam, deposition with homogeneous coverage is difficult. In this work,
homogeneous deposition of size-selected Pt clusters could be performed using Lissajous
scanning method.
In this experimental setup, figure 1, ion beam was focused by einzel
lenses, and then deflected to orthogonal X and Y directions. Ion beamscanning was performed by applying triangle wave to X and Y
electrodes with an irrational frequency ratio fX/fY, and consequently theion trajectory fills a sample surface [1]. Cluster distribution on surfaces
was analyzed using scanning x-ray photoelectron spectroscopy(analysis area < 0.05 mm2). Figure 2 shows the Pt 4f intensity
distribution of Ptn/TiO2(110). Without deflector, figure 2(a) and 2(c), Pt

Fig. 1. Experimental
set up of ion optics
with deflector.

clusters were deposited with a FWHM of 4 mm. Using the ion scanning, figure 2(b) and 2(d),homogeneous distribution could be achieved. Cluster distribution was also analyzed using
scanning tunneling microscopy (STM), and summarized in Table 1. Density of deposited clusters
was independent of position. Thus, homogeneous cluster deposition could be performed using the
Lissajous scanning method.
[1] A. Bazaei, Y. K. Yong, and S. O. R. Moheimani, Rev. Sci. Instrum. 83 (2012) 063701.

Table. 1. Pt atomic density of
Pt15/Al2O3/NiAl(110) estimatedusing STM.

Fig. 2. Pt 4f intensity of (a) Pt4/TiO2(110) prepared without
deflector, and (b) Pt15/TiO2(110) prepared with deflector. (c)Line profile at Y=5 mm of fig. 2(a), and (d) that of fig. 2(b).

Reactivity and catalysis

A71

Time-of-flight mass spectrometry for reaction product detection inheterogeneous catalysis
A. Winbauer1, M. Tschurl1, J. Kiermaier1, U. Boesl1, U. Heiz1
1

Chemistry Department, Technische Universität München, Germany

Mass spectrometry is a very powerful analytical tool for the study of heterogeneous catalysis. It is
often used to study reaction processes by analyzing the reaction products, both in a qualitativeand in a quantitative way.
Typically, mass spectrometers work by using electron impact ionization, where discrimination
between isomers is difficult to achieve. Fragmentation patterns of the isomers must differ to alarge extent to be distinguishable.
A powerful and soft method for selective ionization is REMPI (Resonant Enhanced Multiphoton
Ionization). In this technique a laser of specific wavelength is employed to ionize a single isomerthrough resonant intermediate states. Other isomers are not ionized as they are non resonant at
the energy used [1].
A new experimental setup was built for the study of catalytic reactions on metal clusters supported
on single crystal surfaces under UHV conditions. Custom ion optics were designed to incorporate
the crystal support and enable future desorption-ionization studies and enantioselective laser
mass spectrometry.
In this work we present our experimental setup, in which we combine time of flight mass
spectrometry and resonance enhanced multiphoton ionization for investigation of products formed
via surface reactions. It will thus be possible to examine the selectivity of catalytic reactions on
size selected clusters. Furthermore, we will show first experimental results, for example
wavelength scans and sensitivity tests and first TPD measurements on Pd (643) and Pt (111).
Reference[1] U. Boesl, R. Weinkauf, C. Weickhardt, E. W. Schlag, International Journal of Mass
Spectrometry and Ion Processes 131 (1994) 87-124.

Reactivity and catalysis

A72

H and O adsorption on Fe13Pt42 core-shell nanoparticle
Bheema Lingam Chittari1 and Vijay Kumar,1,2
1

Dr. Vijay Kumar Foundation(VKF), 1969 Sector 4, Gurgaon 122001, Haryana, India

2

Center for Informatics, School of Natural Sciences, Shiv Nadar University, Chithera, Gautam
Budh Nagar - 203207, U.P., India

Nanoalloys of Pt have been shown to exhibit significant improvements in their catalytic properties
compared with pure Pt clusters [1-2]. We have carried out ab initio calculations on Fe13Pt42
nanoparticles having 55 atoms. It has been found that for this size Mackay icosahedral structure
has the lowest energy with the Fe atoms forming an icosahedral core and Pt atoms forming theshell. Note that Fe13 free cluster also tend to have an icosahedral structure while for Pt clusters
triangular faces are preferred [3] and in this nanoparticle structure both these aspects are satisfied.
This core-shell nanoparticle has 48 µB magnetic moments with ferromagnetic coupling. The
magnetic moments on Fe atoms are close to the value in free Fe clusters which is about 3.0 µB per
atom while the magnetic moments on Pt atoms have the value of about 0.21 µB. The Bader charge
analysis shows charge transfer from Fe core to Pt atoms. The charge transfer is more significant
to Pt atoms on the edges. Further calculations have been performed to understand the variation in
H and O adsorption on pure Pt42 nanoparticle and Pt42 surface in the core-shell Fe13Pt42
nanoparticle. We considered H and O atoms on vertex, face, bridge, and edge sites and found thatthe H adsorption on the bridge site shows higher binding energy where it interacts with two Pt
atoms and reduces the magnetic moment significantly to 41 µB. The H adsorption energy on
Fe13Pt42 is 2.39 eV. On the other hand oxygen adsorption is favored on a face site where it
interacts with three Pt atoms and there is an increase in the magnetic moment to 50 µB from thevalue for the free Fe13Pt42 nanoparticle. The O adsorption energy on Fe13Pt42 is 5.81 eV. Similarcalculations of H and O on pure Pt42 nanoparticle show higher binding energies of 2.96 eV and6.40 eV for H and O, respectively. The H and O atoms adsorb, respectively, on an edge and facesite of pure Pt42 similar to the case of Fe13Pt42. These results suggest significant reduction in thebiding energy on Pt when there is Fe core and that the Pt42 in a core shell nanoparticle structure
behaves entirely different from its pure Pt42 structure.
References[1] J. Jang, E. Lee, J. Park, G. Kim, S. Hong and Y. Kown, Sci. Rep. 3 (2013) 2872.
[2] S. Guo, S. Zhang and S. Sun, Angew. Chem. Int. Ed., 52 (2013) 8526.
[3] V. Kumar and Y. Kawazoe, Phys. Rev. B 77, (2008) 205418.
This work has been supported by Asian Office of Aerospace Research and Development.

Reactivity and catalysis

A73

Au38(SR)24 cluster for oxidation catalysis
Bei Zhang,1 Houhua Li,2 Miguel A.G. Hevia, 3 Kaziz Sameh,4 Dawid Wodka,1 Clements Mazet,2Thomas Bürgi1 and Noelia Barrabés1
1

Department of Physical Chemistry, University of Geneva, Geneva, Switzerland

2

Department of Organic Chemistry, University of Geneva, Geneva, Switzerland
3

4

Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain

Depart. of Industrial Engineering, Superior National School of Engineers of Tunis, Tunis, Tunisia
Thiolate protected gold nanoclusters (Aun(SR)m) have been shown catalytically active andselective in several hydrogenation and oxidation reactions[1]. Among them, Au38(SR)24 nanocluster
bears intrinsically chiral features due to the arrangement of the protecting ligands on the surface ofthe cluster, which makes it promising in enantioselective catalysis. As a preliminary test, thestability of Au38(SR)24 nanocluster in the oxidation of sulfide is investigated by in -situ UV-vis
measurements and MALDI. A relation between the catalytic activity and the decomposition of the
Au38 cluster was observed. Previous experience evidences enhancement of catalytic activity ofAun(SR)m clusters through the removal of thiol ligands by thermal treatments [2]. In order tocorrelate the thermal treatment effect on the ligands and metal cluster stability, PM-IRRAS, TG,
TPD/R/O coupled with mass spectrometer, XANESS and TEM studies have been performed. The
influence of the nature of the support material has been evaluated by supporting Au38(SR)24
nanocluster on inert oxide as Al2O3 and reducible oxide as CeO2.

Figure 1. XANESS of insitu thermal treatment of supported Au38(SR)24 cluster
Different interaction, stability and reactivity are observed to depend on the kind of support
employed under thermal treatments. TPD/R/O connected with mass spectrometer studies showeddecomposition of the ligands starting at low temperatures (around 80°C) with two main
fragmentation steps, which may be related with the different staple configurations. XANESS
studies show the formation of cationic Au in the case of using reducible oxide as CeO2.
Reference(s)[1] S. Yamazoe, K Koyasu, and T. Tsukuda, Accounts of Chemical Research, 2014, 47, 816[2] X. Nie, C. Zeng, X. Ma, H. Qian, Q. Ge, H. Xua and R. Jin, Nanoscale, 2013, 5, 5912

Reactivity and catalysis

A74

A new scalable Matrix Assembly Cluster Source (MACS) operating in reflection
mode.
William D Terry, Feng Yin, Jian Liu, Lu Cao, Richard E Palmer.
Nanoscale Physics Research Laboratory, School of physics and Astronomy,
University of Birmingham, Birmingham, B15 2TT, UK
Both fundamental issues [1] and applications [2] are driving the increasing interest in sizeselected clusters. However one of the constraints on the field is the limited flux of size-selectedclusters generally available (for an exception see ref [3]). We have demonstrated the Matrix
Assembly Cluster Source, which employs the ion sputtering of co-condensed cluster atoms andrare gas atoms (e.g. Ar+ and Ar/Ag respectively) operating in transmission mode. Here wedemonstrate cluster samples characterized by HAADF (High Angle Annular Dark Field) STEM
(Scanning Transmission Electron Microscopy) imaging [4], generated by MACS in reflection
mode. We achieve a 1% conversion factor from incident ion beam to cluster beam (~3μA to30nA). Investigation of the incident ion beam and cluster collection angles shows the maximum
cluster yield is found when the sum of the two is 110° (i.e. sum of incident and reflection angles).
The average size of clusters produced (100-600 atoms) is dependent on the concentration ofcluster material in the rare gas matrix. This type of cluster source appears to be scalable and ascale up of cluster production by six or more orders of magnitude to lighter industrial applications
seems feasible ultimately. This maybe achieved using commercially available 100mA sources
which would produce ~1mA at current conversion factors.
References[1] Walt A. de Heer, Rev Mod Phys, 65, 3 (1993) 611-676.
[2] Matake Haruta, Catalysis today, 36, 1, (1997) 153-166.
[3] K Wegner, S Vinati, P Piseri, A Antonini, A Zelioli, E Barborini, C Ducati and P Milani,
Nanotechnology 23 (2012) 185603.
[4] Z. W. Wang, R. E. Palmer, Phys Rev Lett 108 (2012) 245502.

Reactivity and catalysis

A75

Theoretical study of the dehydrogenation of isopropanol on Ni13 cluster
supported on Θ-Al2O3(010) surface
Andrey Lyalin,1 and Tetsuya Taketsugu1,2
1

Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto, Japan2

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Hydrogenation and dehydrogenation reactions are major contributors to many industrial chemical
processes. Many of such processes require using expensive precious metal catalysts. Therefore,
extensive efforts are underway to develop efficient alternatives to traditional catalytic processes [2].
Recently, it has been demonstrated that nickel nanoparticles supported on Θ- and γ-forms of
Al2O3 can serve as effective catalysts for dehydrogenation of secondary alcohols [1]. In spite of thegreat potential of nickel nanoparticles as catalysts for dehydrogenation reactions the mechanismsof such processes are largely not understood.
In the present work we report the results of theoretical investigation of the catalytic activity of Ni 13
cluster supported on Θ-Al2O3(010) surface for the dehydrogenation of isopropanol (C3H8O). The
calculations are carried out using methods of density functional theory (DFT) with the use of PBE
functional and projector augmented wave (PAW) technique as implemented in PWSCF code. It isdemonstrated that dehydrogenation of C3H8O on the free Ni13 cluster is a two-step process withthe first H transfer from the alcohol hydroxyl group followed by C-H bond cleavage. Our
calculations show, that H transfer from OH group of C3H8O to Ni13 is the reaction limiting step withthe barrier of 0.95 eV, while the C-H bond cleavage requires the barrier of 0.41 eV. In the case of
Ni13 clusters supported on Θ-Al2O3(010) the isopropanol molecule adsorbs on top of the surface Al
atom in the close vicinity of the nickel cluster, which results in decrease of the H transfer barrier up
to 0.1 eV due to formation of complementary adsorption sites at metal/support interface.

Figure 1. Energy diagram for dehydrogenation of C3H8O on the free Ni13 (left) and adsorption of
isopropanol in the vicinity of Ni13 cluster supported on Θ-Al2O3(010) surface (right).
References[1] S. E. Davis. M. S. Ide, R. J. Davis, Green Chem. 15 (2013) 17.
[2] K. Shimizu, K. Kon, K. Shimura, S.S.M.A. Hakim, J. Catal. 300 (2013) 242.

A76

Reactivity and catalysis

Chemical Reactivity of Rhodium
and Copper-doped Rhodium Neutral Clusters
Masato Takenouchi, Ken Miyajima, and Fumitaka Mafuné
School of Arts and Sciences, The University of Tokyo, Japan
Catalyst containing rhodium has been extensively studied because of its high reactivity to convert
NOx to N2 and CO to CO2. In our group, Yamada et al. has reported that Rh oxide neutral clusters
have more efficient reactivity with N2O than Rh neutral clusters [1]. In this study, we generated
copper-doped rhodium neutral clusters and investigated the reactivity with N2O.
RhnCum (n = 7-14, m = 0, 1) clusters were generated by the laser ablation of Rh and Cu rods in ahelium carrier gas. The clusters are photoionized by a F2 excimer laser ( =157 nm) and mass
analyzed. RhnCumOp (p = 1-4) were produced by the reaction with N2O. When the concentration of
N2O is sufficiently high, oxygen transfer reactions occur in a following sequence:
RhnCum + N2O → RhnCumO + N2

(1)

RhnCumO + N2O → RhnCumO2 + N2

(2)

Rate constants k1 and k2 were defined for above reactions. Fig.1 shows the rate constants (k1 andk2) of neutral Rhn and RhnCu clusters. It was found that the size-dependence of rate constants
shows the similar trends between Rhn-1Cu and Rhn clusters. The enhancement of secondoxidation step (k2>k1) was found for pure and doped rhodium clusters. From this result, we canconclude that metal atom substitution of a Rh atom by a Cu atom gives no significant change on

Rate Constant (10-13 cm3s-1)

the reactivity of Rhn-1Cu and Rhn clusters.
k1 of Rhn
k1 of RhnCu
k2 of Rhn10

k2 of RhnCu

5

1
7

8

9

10

11

12

13

14

Number of metal atoms
Fig.1 Rate constants k1, k2 of the reactions of neutral Rhn and Rhn-1Cu clusters with N2O
Reference[1] A. Yamada, K. Miyajima, F. Mafuné Phys. Chem. Chem. Phys., 2012, 14, 4188-4195

Reactivity and catalysis

A77

Reduction of N2 on Pd surfaces at low temperatures
Junichi Murakami1, Masayuki Futamata1, Yukimichi Nakao2, Shin Horiuchi2,
Kyoko Bando2, Umpei Nagashima2 and Kazuki Yoshimura3
1

Graduate School of Science and Engineering, Saitama University, Saitama, Japan

2

Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), Tsukuba, Japan
3

Materials Research Institute for Sustainable Development, AIST, Nagoya, Japan

In nature N2 is reduced to NH3 on the FeMo cluster located at the reaction center of thenitrogenase enzyme. On the cluster, N2 is activated in molecular form at room temperature (RT).
This is in marked contrast to the Haber-Bosh process for industrial NH3 production in which theprocess begins with cleaving the strong triple bond of N2 at a very high temperature like 500 °C.
A possibility of directly reducing a N2 molecule to NH3 on a metal surface at low temperatures (LT),in a manner similar to that of nitrogenase, was discussed by Nrskov’s group [1]. However, such a
process has not been experimentally verified. In the symposium we present data showing the
low-temperature reduction of N2 to NH3 takes place on Pd surfaces. Palladium is known todissociate H2 below RT. For N2 adsorption, on the other hand, clean Pd surfaces are known not toadsorb N2. However, it has been reported that once a Pd surface is contaminated with nitrogen, it
easily adsorbs N2 in molecular form at and above RT [2]. Although the nature of the adsorbed N2
has not been elucidated, if N2 molecules adsorbed on Pd surfaces are activated, exposure of thePd surfaces to N2 and H2 may result in reduction of N2, leading to the formation of NH3 at LT.
We used X-ray photoelectron spectroscopy for various Pd samples such as thin Pd films, Pd
plates and Pd fine particles to study interactions of the surfaces with N2 and H2. We found (1) H2
dissociates on the oxidized Pd surfaces at and above RT (as have been reported), (2) N2 isadsorbed by the Pd surfaces probably in molecular form, (3) nitrogen species on Pd surfaces reactwith H from H2 and are reduced to NH3 and (4) the resultant NH3 desorbs from the surface at least
above 70 °C. Thus elementary steps needed to catalytically convert N2 to NH3 with H2 proceed on
Pd surfaces at the low temperatures.
It has been reported that N2 is adsorbed by small Pd clusters [3]. A theoretical calculation for N2
adsorption on a Pd cluster (Pd8) shows N2 is adsorbed with a side-on geometry and activated,which is similar to N2 adsorption on small tungsten clusters [4]. Thus we believe cluster-likestructures on the Pd surfaces are responsible for the N2 adsorption and activation.
References[1] T. H. Rod, A. Logadottir and J. K. Nrskov, J. Chem. Phys. 112 (2000) 5343.
[2] E. Miyazaki, I. Kojima and S. Kojima, Langmuir 1 (1985) 264.
[3] P. Fayet, A. Kaldor and D. M. Cox, J. Chem. Phys. 92 (1990) 254.
[4] J. Murakami and W. Yamaguchi, Sci. Rep. 2, article number 407 (2012).

A78

Reactivity and catalysis

Automated prediction of pathways for single bond activations on small goldclusters: A case study of H2 dissociation on neutral and charged Aunm (n = 1-12,m = 0, ±1)
Min Gao,1 Andrey Lyalin,2 Satoshi Maeda1,2 and Tetsuya Taketsugu1,2
1
2

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

We report the results of a systematic theoretical investigation of single-bond activation pathways
for hydrogen molecule catalyzed by small metal clusters. As it is known, the number of isomers
and adsorption sites on cluster surface increases drastically with the growth in cluster size.
Therefore, a systematic search for the optimal pathways of chemical reactions on metal cluster
surfaces becomes an extremely complicated task and requires urgent development of novelautomated computational methods.
In the present study, a new theoretical approach to find metal-cluster-catalyzed single bondactivation pathways is introduced [1]. The proposed approach combines two automated reaction
path search techniques: the anharmonic downward distortion following (ADDF) and the artificial
force induced reaction (AFIR) methods, developed in our previous works [2]. A simple model
reaction of the H−H bond activation catalyzed by Aunm (n = 1–12, m = 0, ±1) clusters is considered
as an example. Systematic analysis of the structure-dependent reactivity of small gold clusters is
performed. It is demonstrated that the most stable structures of the gold clusters are not always
highlyreactive

as

shown

in

Fig.1.

Therefore, several isomeric structures
must be taken into account for adequate
description of the reaction rates at finite
temperatures. The influence of the charge
state of gold clusters on H2 dissociation is
also investigated. It is shown that excess
of a positive charge on gold cluster canpromote the adsorption and dissociation of
H2 molecule. The proposed approach can
Fig.1 (a) Potential energy profiles for H2 dissociation on

serve as a promising tool for investigationisomers of Au7. (b) Structures along the pathway startingof the chemical reactions catalyzed byfrom the most favorable adsorption geometry. (c)small metal clusters. More details will be

Structures along the three lowest pathways [1].

shown in poster presentation.

References[1] M. Gao, A. Lyalin, S. Maeda, and T. Taketsugu, J. Chem. Theo. Comput. 10 (2014) 1623.
[2] S. Maeda, K. Ohno, and K. Morokuma, Phys. Chem. Chem. Phys.15 (2013) 3683.

A79

Reactivity and catalysis

Preparation and catalytic application of supported silver clusters
Masaru Urushizaki,1 Shinjiro Takano,1 Seiji Yamazoe,1,2 Kiichirou Koyasu,1,2
and Tatsuya Tsukuda1,2
1

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
2

ESICB, Kyoto University, Kyoto, Japan

Silver clusters smaller than 1 nm show size-specific catalysis for hydrogenation of nitroaromatics[1]. In order to understand the origin of size-specific catalysis and to optimize the catalytic
performance of Ag clusters, it is required to synthesize Ag clusters with atomically-precise size.
This work is aimed to synthesize size-controlled Ag clusters on metal oxides by applying themethod we developed for the synthesis of supported Au clusters using thiolate-protected Auclusters

[2].

In

this

work,

we

used

atomically-preciseAgclusters

protectedby

4-melcaptobenzoicacid (MBA), Ag44(MBA)304– [3].
The silver clusters, M4Ag44(MBA)30 (M = Cs and Na),UV-vis spectrum of the products (Fig. 1a) shows that
Ag44(MBA)304–

synthesized.

Then,clusters

were

Ag44(MBA)30

successfully

clusters

wereadsorbed on metal oxides (Al2O3 or TiO2) by mixing
them

in

DMF.

Reflectancespectrumof

Ag44(MBA)30/Al2O3 (Fig. 1b) showed similar features
observed in the absorption spectrum of Ag44(MBA)30

(a)

(b)

(Fig. 1a). This indicates that Ag44(MBA)30 clusters are

Normalized K.M.

theNormalized Absorbancewere synthesized by the method reported in ref [4].

(c)adsorbed on alumina in the intact form. Finally, theAg44(MBA)30/Al2O3 composite was calcined in vacuo at
450 oC to remove the thiolates for catalytic application.

400
400

Reflectance spectrum after the calcination (Fig.1c)

800
600
600
800
Wavelength(nm)
Wavelength (nm)

1000
1000

showed no surface plasmon resonance peak at ~400

Figure.1 (a) UV-vis absorption spectrum ofnm which is characteristic for Ag nanoparticles. This

Ag44(MBA)30, and diffuse reflectance spectra

observation implies that the aggregation of silverof Ag44(MBA)30/Al2O3 (b) before and (c) afterclusters is negligible during the calcination conditions

calcination.

we

employed.

Thiscalcinedclusters

catalyzed

reduction of 4-nitrophenol to 4-aminophenol.
References[1] K.-I. Shimizu et al., J. Catal. 270 (2010) 86.
[2] S. Yamazoe et al., Acc. Chem. Res. 47 (2014) 816.
[3] K. M. Harkness et al., Nanoscale 4 (2012) 4269.
[4] A. Desireddy et al., Nature 501 (2013) 399.

A80

Reactivity and catalysis

A Highly Practical and Reusable Zinc Catalyst for Transesterification
Daiki Nakatake,1 Yuki Yokote,1 Ryo Yazaki1 and Takashi Ohshima1
1

Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, Japan~Introduction~
Ester compounds are ubiquitous in various biologically active natural
products and drugs. General methods for ester synthesis rely on
condensation reagent or reactive acylating reagent, resulting in thegeneration of stoichiometric amounts of unwanted waste. Catalytictransesterification, which generates only lower
alcohols as co-products, is more desirable interms of atom-economy. We recently reported
tetranuclear zinc cluster [Zn4(OCOCF3)6O](Figure 1.), which catalyzed transesterification
under almost neutral conditions with wide functional group tolerance (Scheme 1.) [1]. This zinccatalyst, however, has still much room for improvement, because handling under an inert gas
atmosphere was necessary due to its hygroscopic nature, and the reactions of sterically hindered
2° and 3° alcohols were quite slow.
~This Work~We

developedanewzinc/bis-imidazole ligand complex

highlystable(Scheme 2.).

This zinc complex catalyzed transesterification
reaction without special care regarding air andmoisture with expanded substrate scope [2]. The
complex showed higher catalytic activity than thezinc cluster catalyst itself. In addition, the complex
also catalyzed carbonate formation and oxazoline
formation under the optimized conditions. This
stable nature of the complex made it possible torecover and reuse the catalyst at least five times without significant loss of activity.
References[1a] Iwasaki, T.; Maegawa, Y.; Hayashi, Y.; Ohshima, T.; Mashima, K. J. Org. Chem. 2008, 73,5147. [1b] Ohshima, T.; Iwasaki, T.; Maegawa, Y.; Yoshiyama, A.; Mashima, K. J. Am. Chem. Soc.
2008, 130, 2944. [1c] Maegawa, Y.; Ohshima, T.; Hayashi, Y.; Agura, K.; Iwasaki, T.; Mashima, K.
ACS Catal. 2011, 1, 1178. [2] PCT/JP2014/58876.

A81

Reactivity and catalysis

Thermal stability and reactivity of manganese oxide clusters
Kohei Koyama, Ken Miyajima, and Fumitaka Mafuné
School of Arts and Sciences, The University of Tokyo, Tokyo, Japan
Manganese oxide is known to react with CO and NO in the states of bulk and nanoparticle [1, 2].
In this study, we examined thermal stability and reactivity with CO of cationic manganese oxide
clusters with and without heating process of clusters.
MnnOm+ clusters were generated by the laser ablation of a Mn metal target in 0.1% oxygen seeded
helium carrier gas. Clusters passed through a reaction gas cell and an extension tube heated witha resistive heater before expansion into a vacuum. Fig. 1 shows abundance distribution of MnnOm+clusters (4 ≤ n ≤ 9), indicating MnnOm+ clusters ratio with n : m = 2 : 3 were abundantly formed atroom temperature. As temperature increased to 425 °C, oxygen rich clusters and MnnOm+ clusters
having the composition of n : m = 2 : 3 decreased and instead, oxygen deficient clusters
increased.
Fig. 2 shows abundance ratios of MnnOm+ clusters (n = 8) as a function of temperature. Mn8O11+,
Mn8O12+ and Mn8O14+ were generated at room temperature. As temperature increased, oxygen
rich clusters decreased and oxygen poor clusters increased. For example, Mn8O12+ decreased
while Mn8O10+ increased between 100 °C to 200 °C. It is considered that the oxygen molecule wasdesorbed by heating. MnnOm+ → MnnOm-2+ + O2
Knowing thermal stabilities of MnnOm+ clusters, we examined reactivity with CO. MnnOm+ clusters
forms CO attached products by the reaction with a CO gas at room temperature. As desorption of
CO was observed by heating up to 100 °C, the bonding between CO and cluster is suggested tobe very weak.

Fig. 1 Map of abundance distribution of
MnnOm+ clusters at r.t. and 425 °C.

Fig. 2 Abundance ratio of MnnOm+ clusters(n = 8) increasing temperature .

Reference(s)[1] S. Royer, D. Duprez, Chem. Cat. Chem. 2011, 3, 24.
[2] J. Shan, et al, J. Phys. Chem. C 2013, 117, 8329.

A82

Reactivity and catalysis

Studies on chemical reactions of transition metal clusters with oxygenby using FT-ICR mass spectrometer
Yuta Tobari,1 Kazuki Ogasawara,2 Yoshinori Sato,2 Makoto Saito,2 Shohei Chiashi,2
Shigeo Maruyama,2 and Toshiki Sugai1
1
2

Department of Chemistry, Toho University, Funabashi, Japan

Department of Mechanical Engineering, The University of Tokyo, Tokyo, Japan

Transition metal oxide clusters have been used as+(a) Small Pristine Con+
Co13

industrial catalysts with their unique size effects. However,their size dependence and oxidation reactivity are not well+

Details of experimental apparatus and techniques havebeen described elsewhere [1]. Metal clusters were
produced by a laser vaporization cluster source and were
injected and trapped in a cell under a magnetic field of 6 T.
The trapped clusters were thermalized in several seconds++

Figure 1 shows mass spectra of pristine metal (Mn+: M =(c) Pristine Con

+
Co13

+

(d) Con+O2+

Co13O8+(e) Pristine Fen+
Fe13

and were then exposed to oxygen for 100-1000 ms. The
pressure of O2 of the cell were approximately 5×10-7 Torr.

(b) Small Con+O2
Co9O10Intensity / arb. units

metal clusters with O2 by using FT-ICR.

+

Co7O8

known. Here we present studies on reactions of transition++(f) Fen+O2

Fe13O8Co or Fe) clusters and product metal oxide clusters

400(MnO2m+) with/without O2, respectively. When the pristinecluster (Con+) size distribution was smaller (n = 6-18) in
Fig. 1a, the products were ConO2m+ (n = 5-11, 2m = 6-12)

Fig. 1 Mass spectra of metal andmetal oxide clusters.

800
1200
Mass (m/z)

1600

without any magic numbers (Fig. 1b). The ratios of 2m/n were 1.1-1.3. When the cluster size waslarger (n = 8-28) as shown in Fig. 1c, we can observe a salient magic number of Co13O8+ [2] withthe much lower ratio of 2m/n = 0.6. The production condition of Co13O8+ clarifies that it is derived
from larger parent pristine clusters (Con: n >13) through dissociative oxidation processes [3]. The
intensity analyses also support the production processes with the fact that Co13O8+ is much moreabundant than the pristine Co13+. Figures of 1e and 1f show almost identical cluster distributions of
Fen and FenO2m to those of Con and ConO2m in Figs. 1c and 1d. The results together with theirintensity analyses reveal universal dissociative oxidation processes of transition metal clusters.
Our preliminary reaction rate analyses reveal that the obtained rate constants of Con and Fen (n =7-26) are similar to the Langevin ion-molecule collision rate constant (kL ~ 5.3 × 10-10 cm3 s-1),
which is consistent to the studies on Nin + O2 (n = 2-15) reported by Sugawara and Koga [4].
References[1] S. Inoue and S. Maruyama, Jpn. J. Appl. Phys. 47 (2008) 1931.
[2] Q. Sun, et al., Phys. Rev. B 62 (2000) 8500.
[3] F. Liu, F. X. Li, and P. B. Armentrout, J. Chem. Phys. 123 (2005) 064304.
[4] K. Sugawara and K. Koga, Chem. Phys. Lett. 409 (2005) 197.

A83

Reactivity and catalysis

First-principle study of small nickel cluster structureand hydrogen dissociation on nickel dimer
Pham Thi Nu and Ohno Kaoru
Department of Physics, Graduate School of Engineering, Yokohama National University,
Yokohama 240-8501, Japan
With the aim of improving the active surface to total metal volume ratio, nanoparticles have beenused for years in the field of catalysis. It has been reported that in compared with traditional
supported Ni catalysts, Ni nanocluster catalysts have a potential of having high activity andselectivity particularly in hydrocarbon hydrogenation reactions [1]. Theoretical calculation plays animportant role in predicting the properties of a small cluster.
Recently it has been reported that the hydrogen capacity of hydrogen storage materials such asgraphites and metal hydrides is enhanced by adding a small amount of metal nanoparticles suchas platinum and nickel [2,3]. The phenomenon is described as “hydrogen spillover” process, inwhich the H atoms are created on a metal surface and migrate to the surface of the support.
Using the all-electron mixed basis approach program [4,5], which was developed in our group,
Sahara et al.[6] have performed TDDFT simulations of a simple system composed of nickel dimerand hydrogen molecule. We are studying the stable structure of small nickel clusters. The results
are compared with other theoretical and experimental datain terms of geometric structure and spin multiplicity.
After finding the stable structure of nickel dimer, we
perform the molecular dynamics (MD) simulation ofhydrogen dissociation on nikel dimer. Our MD
simulation result shows a possibility that hydrogenmolecule is dissociated into two hydrogen atoms(see Fig.1).

Fig1. The distance of two hydrogen atoms in MD simulation

References[1] G.Schmid, V.Maihack, F.Lantermann, and S.Peschel, J. Chem.Soc. Dalton Trans. 589 (1996).
[2] Y. W. Li and R. T. Yang, J. Phys. Chem. C 111, 11086 (2007).
[3] M. A. Miller, C. -Y. Wang, G. N. Merrill, J. Phys. Chem. C 113, 3222 (2009).
[4] T. Ohtsuki, K. Ohno, K. Shiga, Y. Kawazoe, Y. Maruyama, and K. Masumoto, Phys. Rev. Lett.
81, 967 (1998); Phys. Rev. B 60, 1531 (1999).
[5] Y. Noguchi, O.Sugino, M. Nagaoka, S.Ishii, and K.Ohno, J. Chem. Phys. 137, 024306 (2012)[6] R. Sahara, H. Mizuseki, M. H. F. Sluiter, K. Ohno, and Y. Kawazoe, RSC Advances 3,12307-12312 (2013)

A84

Reactivity and catalysis

Clusters on La-Ni Mixed Oxides and its Catalytic Performance for Isomerizationof Allylic Alcohols to Saturated Aldehydes
Tamao Ishida,1,5 Jun Aimoto,1 Akiyuki Hamasaki,1 Hironori Ohashi,2 Tetsuo Honma,3 Takushi
Yokoyama,1 Kohei Sakata,4 Mitsutaka Okumura,4 Makoto Tokunaga,1
1
2
3

Department of Chemistry, Kyushu University, Fukuoka, Japan

Faculty of Arts and Science, Kyushu University, Fukuoka, Japan

Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), Hyogo, Japan
4

5

Department of Chemistry, Osaka University, Osaka, Japan

Research Center for Gold Chemistry, Tokyo Metropolitan University, Tokyo, Japan

Isomerization of allylic alcohols into aldehydes is one of the important processes for chemicalindustries. Supported gold nanoparticles have been used for oxidative amination of alcohols(N-alkylation and N-alkylidenation of amines with alcohols), in which hydrogen-borrowing
mechanisms are working.
Inwork,1

this

we

have

attempted this strategy foraTable 1. Isomerization of trans-2-octen-1-ol.
Entry Catalyst
SolventConv.
(%)b
1 Au/NiO
dioxane61
2 Au/La2O3
dioxane8
3 Au/La-Ni-O (1/1)
dioxane98
4 Au/La-Ni-O-H2 (1/1)
dioxane87a

Au 1 mol%, N2 (0.1 MPa), 100 ºC, 24 h.

the
Yield
(%)b
51
3
83
87

Au-catalyzed

isomerizationof

2-propen-1-olandtrans-2-octen-1-ol.

Among

the Au catalysts with simple
oxide

supports,

exhibitedthe

Au/NiOhighestcatalytic activity with excellent selectivity. In addition,a mixed metal oxide support consisting of Ni and La
considerably improved the results. The catalysts
were characterized by X-ray absorption fine structure(XAFS) measurements, which revealed Au in
Au/La-Ni-O-H2 exist as small clusters (coordination
number of Au–Au bond is 6.8). We also carried out
DFT calculation using a Au6 cluster for the catalyst
model.
Reference[1] T. Ishida, J. Aimoto, A. Hamasaki, H. Ohashi, T.
Honma, T. Yokoyama K. Sakata, M. Okumura,
Figure 1. Au L3-edge radial structure
functions of Au/NiO and Au/La-Ni-O.

and M, Tokunaga, Chem. Lett. In press(doi:10.1246/cl.140369).

A85

Reactivity and catalysis

withdraw

Reactivity and catalysis

A86

Release of Oxygen from Copper Oxide Cluster Ions by Heat
Ken Miyajima, Keisuke Morita, and Fumitaka Mafuné
School of Arts and Sciences, The University of Tokyo, Tokyo, Japan
Copper oxide clusters, CunOm+, were prepared in the gas phase by laser ablation of a copper rod
in the presence of 0.5% oxygen in a He carrier gas. The cluster ions were heated up to 1000 K atdownstream of the cluster source (post-heating), and the stoichiometry of CunOm+ (n = 4−19) was
examined using mass spectrometry [1].
As shown in Figures 1a, and b, temperature programmed desorption experiments revealed that anoxygen molecule is released from oxygen-rich CunOm+ (m/n > 2/3), forming CunOm+ (n:m ~ 3:2).
Oxygen molecules are further released from cluster ions to form CunOm+ (n:m ~ 2:1) at the higher
temperatures, suggesting that a Cu atom tends to take +1 charge state at high temperatures (Fig.
1c).
Figure 2 shows that oxygen-rich Cu14O10+ and Cu14O12+ release an oxygen molecule during theheating in the range of 298–550 K and 350–700 K, respectively. Water adducts which areproduced by the impurities in the vacuum chamber are also observed in the temperature of < 600
K. Other CunOm+ clusters also show the similar profiles. It was found that copper oxide clusters
having CunOm+ (n:m ~ 3:2) withstand a high temperature of 500 K.

Figure 1 Mass abundance of CunOm+ clusters: (a) without
heating treatment, (b and c) after heating treatment. Area of
each bubble is proportional to the normalized intensity(CunOm+/∑CunOm+).
m

Figure 2 Temperature programmed desorption spectra of
Cu14Om+ clusters. Open symbols correspond to the water
adducts.
Reference[1] K. Morita, K. Sakuma, K. Miyajima, F. Mafuné, J. Phys.
Chem. A 117 (2013) 10145-10150.

A87

Reactivity and catalysis

Regenerative synthesis of copper nanoparticles on TiO2 nanoparticles byphotoreduction
Naoki Nishida, Takuya Aoki, and Hideki Tanaka
Department of Applied Chemistry, Chuo University, Tokyo, Japan
Copper nanoparticle has attracted interest due to their potential contribution to a wide variety ofareas, including optical and electronic applications. Meanwhile, regenerative property of synthesis
process of nanoparticles is an important subject in science and technology because of deeply
understanding of growth and decomposition mechanism of nanoparticles besides sustainability ofmetal resources. In this study, we investigated the regenerative synthesis of copper nanoparticle
on titanium oxide through the photoreduction of copper acetate.
The synthesis of copper nanoparticles by photoreduction was carried out using a similar method
reported previously [1,2]. Copper acetate powder and titanium oxide nanoparticles dispersion
were dissolved in ethanol. The mixed solution was photoirradiated using a high-pressure Hg lamp
for 24 h at room temperature.
Figure 1 shows extinction spectra with photoirradiation at 24 h. A peak of surface plasmon bandfor copper nanoparticles is observed at ~580 nm. When the copper nanoparticles solution was
exposed to fresh air, the signal of surface plasmonband was decreaced. Additionally, surface plasmon
peaks were red shift with exposure time. These
coincidences imply that the copper nanoparticles were
etched by exposure to fresh air. Furthermore, when thedecomposed solution was re-photoirradiated, surface
plasmon band for copper nanoparticles were observed
again.

Itwas

provedthattheformation

anddecomposition of copper nanoparticles could bealternately repeated by using the present method.
These results have inspired us to develop applications
for novel catalysts recycled by photoirradiation andopticaldevicesthatcanphotoirradiation and air exposure.

beswitched

byFigure 1. Extinction spectra of copper
nanoparticles for air-exposure time.

References[1] N. Nishida, A. Miyashita, N. Hashimoto, H. Murayama and H. Tanaka, Eur. Phys. J. D 63
(2011) 307.
[2] N. Nishida, A. Miyashita, T. Tsukuda and H. Tanaka, Chem. Lett. 42 (2013) 168.

A88

Reactivity and catalysis

Stoichiometry of cationic and anionic vanadium oxide clusters
analyzed by ion mobility-mass spectrometry
Jenna W.J. Wu, Ryoichi Moriyama, Hiroshi Tahara, Keijiro Ohshimo, and Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki,
Aoba-ku, Sendai 980-8578, Japan
Bulk vanadium oxides are widely studied due to their various usages in industry as oxidization
catalyst. Structures and reactions of small vanadium oxide clusters, VmOn+/-, are also being
studied intensively. In this study, stable compositions of anionic and cationic vanadium oxide
clusters up to m = 60 are identified and discussed.
Vanadium oxide cluster ions generated by laser vaporization were injected into a drift cell withan energy of 250 eV by a pulsed electric field. Collision-induced dissociations occur at theentrance of the cell, then the product ions pass through the cell by applied electrostatic field. The
ions were detected in the later TOF mass-analysis process.
The stoichiometry components have a dependency on parity of the vanadium atom numbers,
which is caused by the open and closed shell effect in the formation of clusters [1]. Odd numbered
VmOn+/- clusters are closed-shell species with fully oxidized vanadium atoms; on the contrary evennumbered VmOn+/- clusters are open-shell species containing uneven number of electrons.
In cationic odd numbered vanadium oxide clusters, (VO2)(V2O5)x+ and (VO)(V2O5)x+ are mainly
observed (listed according to the level of intensity);
also, (V2O4)(V2O5)x+ and (V2O5)x+ are observed foreven numbered clusters as shown in Figure 1. Similar
to the cations, the anions also have several stablespecies corresponding to the number of vanadium
atoms,

yet,theyexhibitin

one-oxygenrichstoichiometry. For the odd numbered vanadium oxides(VO3)(V2O5)x and (VO2)(V2O5)x are observed; theeven numbered are (V2O5)x and (V2O4)(V2O5)x.
The above ions are in good agreement withphotodissociation products for the small vanadiumoxide clusters where m < 10 [2]. Additionally, therelatively stable species observed are due to terminal
oxygen dissociation in the cluster formation andinteraction

processes.

Thesecharacteristics

areapplicable to sizes up to m = 60.
Figure 1. Cationic vanadium oxide clusters witheven and odd numbered stoichiometry.

References[1] G. Santambrogio, M. Brummer, and K. R. Asmis, Phys. Chem. Chem. Phys. 10 (2008) 3992.
[2] K. S. Molek, T. D. Jaeger, and M. A. Duncan, J. Chem. Phys. 123 (2005) 144313.

POSTER SESSION B
September 11th, Thursday
16:30 - 18:30
Electron correlation: magnetism and superconductivity
Energy-related topics & Environmental studies
Optical properties and plasmonics
Carbon based nanomaterials
Carbon-based
Device-oriented topic
Structure and thermodynamics
Reactivity and catalysis

B1-B11B12-B15
B16-B26
B27 B35
B27-B35
B36-B40
B41-B63
B64-B89

B1
B2

B3

B4

B5
B6

B7
B8

B9

B10

B11

B12

Anomalous Hall Effect in Uniform Fe nanocluster-Assembled Films
Junbao Wang1, Wenbo Mi2, Laisen Wang1, Qinfu Zhang1, Dongliang Peng1 ; 1
Xiamen University, 2 Tianjin University
Magnetism and exchange interaction in small Terbium clusters
Andrei Kirilyuk1, Saurabh Ghosh2,3, Biplab Sanyal3, Lars Peters1, Chris van Dijk1,
John Bowlan4, Anna Delin3, Igor Di Marco3, Walt de Heer4, Mikhail I. Katsnelson1,
Olle Eriksson3 ; 1 Radboud University Nijmegen, IMM, 2 Cornell University, 3
Uppsala University, 4 Georgia Institute of Technology
Relation between valence of iron ions in maghemite nanoparticles and theirsaturation magnetization
Keita Kobayashi, Kazunari Nojiri, Tomoyuki Terai, Tomoyuki Kakeshita , Hidehiro
Yasuda ; Osaka University
Magnetization and Mössbauer Study of Partially Oxidized Iron cluster Films
Deposited on HOPG
Nils Tarras-Wahlberg1, Saeed Kamali2, Mats Andersson1,3, Christer Johansson4,
Arne Rosen1,5 ; 1 Gothenburg University and Chalmers University of Technology,
2
University of California, Davis, 3 Chalmers University of Technology, 4 Acreo
Swedich ICT AB, 5 Gothenburg University
Term rules for small aluminum clusters
Daisuke Yoshida, Hannes Raebiger ; Yokohama National University
Self-doping of ultrathin insulating films by transition metal atoms
Z. Li1, H.-Y. T. Chen2, K. Schouteden1, L. Giordano2, M. I. Trioni3, E. Janssens1,
V. Iancu1, C. Van Haesendonck1, P. Lievens1, G. Pacchioni2 ; 1KU Leuven,
2
Università di Milano-Bicocca, 3CNR - National Research Council of Italy, ISTM
withdraw
Probing the phonon density of states and its effect on superconductivity in
Sn nanoparticles, nano-islands, and cluster-assembled films
K. Houben1, S. Couet1, J. Jochum1, D. Pérez1, M. Bisht1, M.Trekels1, T. Picot1,
R. Rüffer2, M.Y. Hu3, S.A. Brown4, F.M. Peeters5, P. Lievens1, A. Vantomme1, K.
Temst1, M.J. Van Bael1 ; 1 KU Leuven 2 European Synchrotron Radiation Facility(ESRF), 3 Argonne National Laboratory, 4 University of Canterbury, 5 Universiteit
Antwerpen
X-ray absorption spectroscopy of free, size selected, singly metal doped
silicon clusters
Vicente Zamudio-Bayer1,2, Linn Leppert3, Konstantin Hirsch2,4, ArkadiuszŁawicki2, Andreas Langenberg2,4, Jochen Rittmann2,4, Martin Kossick2,4, Marlene
Vogel2,4, Robert Richter2,4, Thomas Möller4, Akira Terasaki5,6, Stephan Kümmel3,
Bernd von Issendorff1, Julian Tobias Lau2 ; 1Universität Freiburg, 2Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 3 Universität
Bayreuth, 4 Technische Universität Berlin, 5 Toyota Technological Institute, 6
Kyushu University
Magnetic moments of chromium-doped gold clusters: The Anderson
impurity model in finite systems
K. Hirsch1, 2, V. Zamudio-Bayer5, A. Langenberg1, 2, M. Niemeyer1, 2, B.
Langbehn1, 2, T. Möller2, A. Terasaki3, 4, B. v. Issendorff5, J. T. Lau1 ;1
IHelmholtz-Zentrum Berlin für Materialien und Energie GmbH, 2Technische
Universität Berlin, 3Toyota Technological Institute, 4Kyushu University,
5
Universität Freiburg
Superconducting properties of nanoparticles and small clusters
T. Picot1, H. Wang1, K. Houben1, A. Hillion1, S. Bals2, S.A. Brown3, E. Janssens1,
P. Lievens1, A. Vantomme2, K. Temst1, M.J. Van Bael1 ; 1 KU Leuven, 2
Universiteit Antwerpen, 3 University of Canterbury
Formic Acid Oxidation Catalytic Properties of Pd Nanoparticles Preparedby Physical Vapor Deposition
L.S. Wang, M. Lei, J.B. Wang, C.Y. Zou, D.L. Peng ; Xiamen University

B13

B14

B15

B16

B17
B18

B19

B20
B21

B22

B23

B24

B25

Fabrication of Si nanoparticles from Si swarf and the application tohydrogen generation source
Taketoshi Matsumoto1, Katsuya Kimura1, Kentaro Imamura1, Masao Takahashi1,
Yayoi Kanatani2, Tohru Higo2, Hikaru Kobayashi2 ; 1 Osaka University,
CREST-JST, 2 Nisshin Kasei Co., Ltd., CREST-JST
Structural and optical properties of “Cauliflower” silicon nanoparticles
Wingjohn Tang1, Joren Eilers1, Marijn van Huis1, Da Wang1, Ruud Schropp2,
Andries Meijerink1, Alfons van Blaaderen1, Marcel Di Vece1 ; 1Utrecht University,
2
ECN, TU/e
Sulfuric acid clusters in atmospheric particle formation: insights fromcomputational approaches
Henning Henschel, Oona Kupiainen-Määttä, Theo Kurtén, Ville Loukonen, Tinja
Olenius, Hanna Vehkamäki ; University of Helsinki
Photoluminescence properties of Si nanoparticles fabricated from Si swarf:
fluorescence enhancement by organic molecules
Masanori Maeda, Taketoshi Matsumoto, Hikaru Kobayashi ; Osaka University,
CREST, Japan Science and Technology Agency
Ag44SR30: What comes after the structure is solved?
Lars Gell, Hannu Häkkinen ; University of Jyväskylä
Information on Quantum States Pervades the Absorption Spectra of the
Au144 (SR)60 Nanocluster
H.-Ch. Weissker1,2, V.D. Thanthirige4, K. Kwak5, D. Lee5, G. Ramakrishna4, R.L.
Whetten3, X. López-Lozano3 ; 1 Aix-Marseille Univ., CNRS, 2 European
Theoretical Spectroscopy Facility, 3 The University of Texas at San Antonio, 4Western Michigan University, 5 Yonsei University
Preparation of non-toxic gold submicron-sized particles using
laser-induced melting in liquids
Takeshi Tsuji1, Yuuma Higashi2, Masaharu Tsuji2, Yoshie Ishikawa3, Naoto
Koshizaki3 ; 1 Shimane University, 2 Kyushu University, 3AIST, 4Hokkaido
University
Polymer-protected fluorescent platinum nanoclusters and their application
Xin Huang, Hidekazu Ishitobi, Yasushi Inouye ; Osaka University,
Electrochemical Reactions and Spectral Changes of Gold-Silver Core-shell
Nanorods on ITO Plates
Yuki Hamsaki1, Naotoshi Nakashima1,2,3, Yasuro Niidome1,2,4 ; 1 Kyushu
University, 2 I2CNER WPI, Kyushu University, 3 CREST, 4 Kagoshima University(Present Affilication)
Novel thiolate-protected gold clusters with sub-2 nm sized and fcc cores:
synthesis and optical property
Shinjiro Takano1, Seiji Yamazoe1,2, Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1
The University of Tokyo, 2 Kyoto University
Gold ultrathin nanowires and nanorods: First observation of surface
plasmon resonance
Ryo Takahata1, Seiji Yamazoe1,2, Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1 The
University of Tokyo, 2 Kyoto University
Controlled formation of highly luminescent silver clusters in zeolite
matrices via high-brilliance soft X-ray irradiation
Didier Grandjean1, Eduardo Coutino-Gonzalez1, Maarten Roeffaers1, Kristina
Kvashnina2, Eduard Fron1, Bert Sels1, Johan Hofkens1, Peter Lievens1 ; 1 KU
Leuven, 2 ESRF
One-step
Synthesis
andCharacterizationofBenzenthiol
Derivative-protected Gold Clusters
Takuya Ishida1, Yukina Takahashi1, Hiroaki Okamura2, Junichi Kurawaki2, Sunao
Yamada1 ; 1 Kyushu University, 2 Kagoshima University

B26
B27

B28
B29

B30

B31

B32

B33
B34

B35

B36
B37

B38

Ultrafast Strong Field Ionization of Small Metal Clusters
Dennis Dieleman, Valeriy Chernyy, Theo Rasing, Andrei Kirilyuk ; Radboud
University
Monocarbon cationic cluster synthesis from methane-nitrogen mixturesembedded in He nanodroplets and their calculated binding energies
Iogann Tolbatov, Sylwia Ptasinska, Daniel M. Chipman ; University of Notre
Dame
Genuinely amorphous carbon produced from explosive nano acetylide
Ken Judai, Naoyuki Iguchi, Yoshikiyo Hatakeyama ; Nihon University,
Evaluation of the ratio of metal/semiconductive single-wall carbon
nanotubes separated in two immiscible aqueous solution phases byutilizing Raman spectroscopy
Shinzo Suzuki1, Naoki Kanazawa1, Akira Ono2, Yohji Achiba3 ; 1 Kyoto Sangyo
University, 2 Kanagawa University, 3 Tokyo Metropolitan University
Growth of single-wall carbon nanotubes on the porous glass (PG) sheet byusing ACCVD technique
Shinzo Suzuki1, Kyohei Nagao1, Yosuke Ito 1, Nobuaki Ito 2, Hiroshi Nagasawa3,
Yohji Achiba4 ; 1 Kyoto Sangyo University, 2 JAIST, 3 Nano-support Co. Ltd., 4Tokyo Metropolitan University
Analysis of the products of single-walled carbon nanotube growth with theaid of density functional theory calculations
Arne Rosén1, Yunguo Li2, J. Andreas Larsson4, Hamid Reza Barzebar3, ThomasWågberg3 ; 1University of Gothenburg, 2Royal Institute of Technology, 3Umeå
University, 4Luleå University of Technology
Bonding and Spin-polarized Transport of Co Atomic Chain on Graphene with
Topological Line Defects
Cheng-huan Jiang1, 2, Gui-xian Ge1, Jian-guo Wan1, Guang-hou Wang1 ; 1Nanjing University, 2 Communication University
Metallic sp2 carbon nanomaterials with octagons showing high density ofstates at the Fermi level: A first principles study
Yusuke Noda, Shota Ono, Kaoru Ohno ; Yokohama National University
Simultaneous formation of fullerenes and polyynes by laser ablation in thegas phase at room temperature
Hitomi Endo1, Yuki Taguchi1, Yurika Abe1,Tomonari Wakabayashi2, Takeshi
Kodama1, Yohji Achiba1, Haruo Shiromaru1 ; 1 Tokyo Metropolitan University, 2
Kinki University
Pressure dependence of production of carbon nanotubes by
High-temperature Pulsed-arc Discharge
Hayato Kikuchi, Atsushi Shimaya, Hiroki Koizumi, Ryota Jinnouchi, Katsuhide
Terada, Toshiki Sugai ; Toho University
Ligand exchange reactions on transition metal oxo clusters andapplications in materials chemistry
Johannes Kreutzer, Ulrich Schubert ; Vienna University of Technology
Extending the Sizes and Charge States of Polyanionic Metal Clusters
Steffi Bandelow1, Franklin Martinez1,2, Gerrit Marx1, Lutz Schweikhard1, Albert
Vass1 ; 1 Ernst-Moritz-Arndt University Greifswald, 2 present address: Universityof Rostock
Surface immobilization of gas-phase-synthesized nanoclusters toward
construction of nanoelectronics
Masato Nakaya1,2, Takeshi Iwasa1,2, Hironori Tsunoyama1,2, Toyoaki Eguchi1,2,
Atsushi Nakajima1,2 ; 1Nakajima Designer Nanocluster Assembly Project, JST, 2
Keio University,

B39

B40
B41
B42
B43

B44
B45

B46

B47
B48

B49

B50

B51

B52
B53

Generation of small and stable Si nanoparticles using a liquid jet
co-deposition method
Gediminas Galinis, Oliver Youle, Hanieh Yazdanfar, Mike J. McNally, Mumin M.
Koç, Gauthier Torricelli, Mark Watkins, Klaus von Haeften ; University ofLeicester
Enhanced quantum coherence in graphene by Pd cluster deposition and its
zero-temperature saturation
Fengqi Song, Junhao Han, Yuyuan Qin, Guanghou Wang ; Nanjing University
The hydrogen Bonded Networks in Hydrated Halogen Anions
Chiaki Ishibashi1, Suehiro Iwata2, Kaoru Onoe1, Hidenori Matsuzawa1 ; 1 Chiba
Institute of Technology, 2Keio University
Formation of regular polyicosahedral structure during growth of large
Lennard-Jones clusters from their global minimum
Wieslaw Polak ; Lublin University of Technology
Structures and dielectric properties of neutral lead clusters
D.A. Götz1, A. Shayeghi1, R.L. Johnston2, P. Schwerdtfeger3, R. Schäfer1 ; 1
Technische Universität Darmstadt, 2 University of Birmingham, 3 Massey
University
Fabrication of Ag cluster by a novel laser ablation of nanocolloid target
Teppei Nishi, Yusuke Akimoto, Shuji Kajiya, Kosuke Kitazumi, Naoko Takahashi,
Yoshihide Watanabe ; Toyota Central R&D Labs., Inc.
Solvation Chemistry of Water-Soluble Thiol-Protected Gold Nanocluster
Au102 from DOSY NMR Spectroscopy and DFT Calculations
Tanja Lahtinen, Kirsi Salorinne, Sami Malola, Jaakko Koivisto,
Hannu
Häkkinen ; University of Jyväskylä
Size-dependent structures of iron oxide cluster ions studied by ion mobility
mass spectrometry
Tatsuya Komukai, Ryoichi Moriyama, Keijiro Ohshimo, uminori Misaizu ; Tohoku
University
Fabrication of Rh nanoframes through dissolution of Au cores of Au@Rh
core-shell nanorods by the addition of HCl
Yukinori Nakashima, Masashi Hattori, Masaharu Tsuji ; Kyushu University
Effect of Core Size on Au-Pt Core-Shell Nanoparticles for Oxygen
Reduction Reaction
Saki Hirose1, Yoshikiyo Hatakeyama2, Ken Judai2, Takeshi Morita1, Keiko
Nishikawa1 ; 1Chiba University, 2Nihon University
Melting of Weakly-Bound Systems by Monte Carlo Simulations –Applications to Mercury and Argon under High Pressure
Elke Pahl1, Jonas Wiebke1, Peter Schwerdtfeger1, Florent Calvo2 ; 1 Massey
University Auckland, 2 ILM
Design of Three-shell Icosahedral Matryoshka Clusters A@B12@A20 (A = Sn,
Pb; B = Mg, Zn, Cd, Mn) Including a New Type of Magnetic Superatoms
Xiaoming Huang 1, Jijun Zhao *1,2, Yan Su 1, Zhongfang Chen 3, R. Bruce King *4 ;1
Dalian University of Technology, 2 Beijing Computational Science ResearchCenter, 3 University of Puerto Rico, 4 University of Georgia
Structures, electronic and magnetic properties of Fe2Gen- and Cr2Gen(n=3-12) clusters from DFT calculations and photoelectron spectra
Xiaoqing Liang1, Xiaoming Huang1, Jijun Zhao1*, Hongguang Xu2, Weijun
Zheng2 ; 1Dalian University of Technology, 2 Chinese Academy of Sciences
Geometric, electronic, and magnetic structure of FexOy clusters
Remko Logemann, Gilles de Wijs, Mikhail Katsnelson, Andrei Kirilyuk ; Radboud
University Nijmegen
Redispersibility of Solid State Cysteine-Capped CdSe Nanoparticles
Depending on pH Values of These Aqueous Solution
Takuya Kurihara, Yasuto Noda, K. Takegoshi ; Kyoto University

B54
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B56
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B58

B59

B60
B61

B62

B63
B64

B65
B66

B67

Structural Stability in icosahedral Ni-Zr-Nb ternary clusters
Nobuhisa Fujima1, Toshiharu Hoshino1, Mikio Fukuhara 2 ; 1 Shizuoka University,
2
Tohoku University
Synthesis of Porphyrin-face Coordinated Au Clusters and Their Interfacial
Interaction
Masanori Sakamoto1,2, Daichi Eguchi1, Toshiharu Teranishi1 ; 1 Kyoto University,
2
PRESTO-JST
Origin of Magic Stability for Aluminum-Boron Binary Nanoclusters
Tomomi Nagase 1, Shoichiro Suga1, Hironori Tsunoyama1,2, Atsushi Nakajima1,2 ;1Keio University, 2Nakajima Designer Nanocluster Assembly Project, JST-ERATO
Geometrical structures of vanadium oxide cluster ions studied by ion
mobility mass spectrometry
Ryoichi Moriyama, Jenna W. J. Wu, Hiroshi Tahara, Keijiro Ohshimo, Fuminori
Misaizu ; Tohoku University
Synthesis of stable gold clusters face-coordinated by porphyrin derivatives
containing disulfide groups
Daichi Eguchi1, Masanori Sakamoto1,2, Toshiharu Teranishi1 ; 1 Kyoto University,
2
JST-PRESTO
Observation of halogen adsorbates on magic numbered gold clusters
stabilized by polyvinylpyrrolidone
Setsuka Arii1, Satoru Muramatsu1, Seiji Yamazoe1, 2,Kiichirou Koyasu1, 2, Tatsuya
Tsukuda1, 2 ; 1 The University of Tokyo, 2 Kyoto University
Secondary ion emission from micro droplets induced by fast ion impacts
Takuya Majima1, Tatsuya Nishio2, Kensei Kitajima2, Yoshiki Oonishi 2, Hiroki
Ueda2, Hidetsugu Tsuchida1, Akio Itoh1,2 ; 1 Kyoto University, 2 Kyoto University
Drift time measurements of H3O+ hydrate formed by NO+ injection into drift
tube filled with H2O/buffer gas at low temperatures
Hiroshi Hidaka1, Yoichi Nakai2, Takao M. Kojima3, Naoki Watanabe1 ; 1 Hokkaido
University, 2 RIKEN Nishina Center for Accelerator-Based Science, 3 Atomic
Physics Laboratory, RIKEN
Solid-state absorption properties and crystal structures of di-alkynylated
octanuclear gold clusters
Mizuho Sugiuchi, Naoki Kobayashi, Yukatsu Shichibu, Katsuaki Konishi ;Hokkaido University
Helium droplets doped with sulfur and C60
Martina Harnisch1, Nikolaus Weinberger1, Stephan Denifl1, Paul Scheier1, Olof
Echt1,2 ; 1 University of Innsbruck, 2 University of New HampshireSize- and Isomer-Dependent Reactivity of Nickel Oxide Cluster Ions Studied
by Ion Mobility Mass Spectrometry
Keijiro Ohshimo, Shohei Azuma, Tatsuya Komukai, Ryoichi Moriyama, Fuminori
Misaizu ; Tohoku University
Protected but Accessible: Oxygen Activation by Calixarene-stabilized
Undecagold Cluster
Xi Chen, Hannu Häkkinen ; University of Jyväskylä
The origin of the high selectivity and catalytic activity of small ruthenium
clusters in the methanation of CO
Sandra M. Lang1, Thorsten M. Bernhardt2, Marjan Krstić2, Vlasta
Bonačić-Koutecký2,3 ; 1 University of Ul, 2 University of Split
3
Department of Chemistry, Humboldt-University Berlin
Low-temperature catalytic activity of CO oxidation driven by strong
electronic interaction between Pt-Ag bi-element cluster and Si surface
Hisato Yasumatsu1, Nobuyuki Fukui2 ; 1 Toyota Technological Institute, 2 Genesis
Research Institute, Inc.

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B81

B82

Dynamics of truly monodisperse cluster catalysts under the STM
Y. Fukamori, F. Knoller, M. König, F. Esch, U. Heiz ; Technische Universität
München
Effects of Ir addition on gas-phase and supported Au nanoclusters towards
catalytic CO oxidation
Laura Michelle Jiménez-Díaz, Luis Antonio Pérez ; Universidad Nacional
Autónoma de México
Theoretical investigation for isomerizaiton of allyl alcohol over Au cluster
Mitsutaka Okumura1,2, Kohei Tada1, Kohei Sakata1, Hiroaki Koga2 , Takashi
Kawakami1, Shusuke Yamanaka1 ; 1 Osaka University, 2 Kyoto University
Synthesis of Ag@Pd/TiO2 catalysts in an aqueous solution for thehydrogen generation from decomposition of formic acid at room
temperature
Daisuke Shimamoto, Masashi Hattori, Takeshi Daio , Masaharu Tsuji ; Kyushu
University
Reaction of aluminum cluster cations with a mixture of O2 and H2O gases:
Formation of hydrated-alumina clusters
Masashi Arakawa, Kei Kohara, Akira Terasaki ; Kyushu University
Adsorption and catalytic activation of the molecular oxygen on the metal
supported h-BN
Andrey Lyalin1, Akira Nakayama1,2, Kohei Uosaki3, Tetsuya Taketsugu1,2 ; 1 Kyoto
University, 2 Hokkaido University, 3 GREEN, NIMS
Reductive Activation of CO2 by Cobalt Cluster Anions
Akimaro Yanagimachi1, Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1 The
University of Tokyo, 2 Kyoto University
Theoretical study on the isomerization of small gold clusters induced by O2
adsorption
Min Gao1, Daisuke Horita1, Yuriko Ono1, Andrey Lyalin2, Satoshi Maeda1,2,
Tetsuya Taketsugu1,2 ; 1 Hokkaido University, 2 Kyoto University
Materials Development for Realization of Carbon-Neutral Energy Cycles
Miho Yamauchi ; Kyushu University, JST-CREST
Adsorption and decomposition of NO on foreign metal-doped copper
cluster cations
Shinichi Hirabayashi1, Masahiko Ichihashi2 ; 1 Genesis Research Institute, Inc., 2
Toyota Technological Institutewithdraw
Base catalysis of [Nb6O19]8– and [Nb10O28]6–
Shun Hayashi1, Seiji Yamazoe1,2, Kiichirou Koyasu1,2, Tatsuya Tsukuda1,2 ; 1 The
University of Tokyo, 2 Kyoto University
FT-ICR study of chemical reaction of acetonitrile molecules on cobalt
clusters
Kazuki Ogasawara1, Yuta Tobari2, Yoshinori Sato1, Makoto Saito1, Shohei
Chiashi1 , Toshiki Sugai2, Shigeo Maruyama1 ; 1 The University of Tokyo, 2 Toho
University
Gold Nanoparticle-Catalyzed C–H Bond Functionalization for Biaryl
Synthesis
Yoshiyuki Mise1, Shohei Aikawa1, Tamao Ishida1,4, Ryota Akebi1, Akiyuki
Hamasaki1, Hironori Ohashi1, Tetsuo Honma2, Tetsuro Tsuji3, Yasushi
Yamamoto3, Mitsuru Miyasaka3, Takushi Yokoyama1, Makoto Tokunaga1 ; 1
Kyushu University, 2 JASRI/SPring-8, 3 UBE Industries Ltd., 4 Tokyo Metropolitan
University
Gas Phase Modeling of the Catalytically Active Centers in Iron Sulfur
Proteins
Heiko Heim, Thorsten M. Bernhardt, Sandra M. Lang ; University of Ulm

B83
B84
B85

B86

B87

B88

B89

Thermal stability and reactivity with CO molecules of cerium oxide andgold-appended cerium oxide clusters
Toshiaki Nagata, Ken Miyajima, Fumitaka Mafuné ; The University of Tokyo
Enhancement of photocatalytic activity of TiO2 nanoparticles by addition of
Ag nanoparticles
Mari Yonemura, Naoki Nishida, Hideki Tanaka ; Chuo University
Towards the Creation of Functionalized Metal Nanoclusters and Highly
Active Photocatalytic Materials Using Thiolate-Protected Magic Gold
Clusters
Yuichi Negishi ; Tokyo University of Science
Formation and structural analysis of composite of Ag nanoplates with TiO2
nanoparticles
Hiroki Nanjyo, Ken Iwai, Naoya Kinoshita, Naoki Nishida, Hideki Tanaka ; Chuo
University
Instantaneous cooling of metal clusters by collision with rare gas clusters –Incorporation mechanism of a cobalt cluster ion into an argon cluster
Hideho Odaka1, Masahiko Ichihashi2 ; 1 East Tokyo Laboratory, Genesis
Research Institute, Inc., 2 Toyota Technological InstituteSurface oxide luminescence of Silicon nanoclusters
Hanieh Yazdanfar, Gediminas Galinis, Mike J. McNally, Mumin. M. Koç, Oliver
Youle, Gauthier Torricelli, Mark Watkins, Klaus von Haeften ; University ofLeicesterAutoionization in cluster Coulomb explosion studied by magnetic
time-of-flight ion imaging
C. Schaal, R. Irsig, S. Skruszewicz, J. Tiggesbäumker, K.-H. Meiwes-Broer ;Universität RostockB1

Electron correlation: magnetism and superconductivity

Anomalous Hall Effect in Uniform Fe nanocluster-Assembled Films
Junbao Wang,1 Wenbo Mi,2 Laisen Wang1 Qinfu Zhang1 and Dongliang Peng1
1

Department of Materials Science and Engineering, Xiamen University, Xiamen, China
2

Department of Applied Physics, Tianjin University, Tianjin, China

Recently, the anomalous Hall effect (AHE) in ferromagnets has gained increasing attentions due
to its controversial mechanisms [1,2]. Usually, in some heterogeneous systems the deviations
from the scaling law (  xy   xx , =1, 2) between the saturated AHE resistivity (  xy ) andAAlongitudinal resistivity (ρxx) were observed. However, so far few attempts have been made to study
the relation between the different γ and the size distribution of nanoparticles. In this work, theuniform Fe nanocluster-assembled films with different thicknesses (ta=160-1200 nm) wereprepared by plasma-gas-condensation method. By Quantum Design physical property
measurement system, we measured the magnetic and electrical transport properties of thesamples ranging from 5 to 375 K. As shown in the inset of Fig. 1, ρxy was calculated from Vxyta/I,
where Vxy is the transverse voltage, I the applied DC current. It is found that the Fe nanoclusters
possess “core-shell” structure. Compared with bulk Fe, four-order (~2.4 10-8 ΩcmG–1)
enhancement of the AHE coefficients was observed for the film with ta=1200 nm at 300 K. The xyA firstly increases and further decreases with the increasing temperature in the range of 5-375
A
K. Moreover,  xy decreases with the increase of ρxx in log-log scales and following a new scalingA
relation of log(  xy /  xx )  a0  b0 log  xx (Fig. 1).

Fig. 1 The plot of log(  xy /  xx )  log  xx for the film with ta=1200 nm.
A

In inset shows schematic of contact arrangement and Hall effect measurements.
Reference(s)[1] P. He, L. Ma, Z. Shi, G. Y. Guo, J. G. Zheng, Y. Xin and S. M. Zhou, Phys. Rev. Lett, 109 (2012)066402.
[2] Z. B. Guo, W. B. Mi, A. Manchon, J. Q. Li, B Zhang, P. G. Barba and X. X. Zhang, Appl. Phys.
Lett, 102 (2013) 062413.

Electron correlation: magnetism and superconductivity

B2

Magnetism and exchange interaction in small Terbium clusters
Andrei Kirilyuk1, Saurabh Ghosh2,3, Biplab Sanyal3, Lars Peters1, Chris van Dijk1, John Bowlan4,
Anna Delin3, Igor Di Marco3, Walt de Heer4, Mikhail I. Katsnelson1, and Olle Eriksson3
1

Radboud University Nijmegen, IMM, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands
2

School of Applied and Engineering Physics, Cornell University, Ithaca, New York 14853, USA

3

Department of Physics and Astronomy, Uppsala University, Box 516, 751 20 Uppsala, Sweden
4

School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332, USA

The rare-earth metals have similar crystal structures, which arise from the relatively unchanged
electronic structure of the valence shells as the localised 4f-shell is being filled [1]. In spite of this,their magnetic structures vary significantly [2]. This is directly related to the mechanism of theexchange interaction in these materials where the spin-polarized 4f wavefunctions of each atom
do not overlap but are responsible for a large magnetic moment. In contrast, the spd electrons aredelocalized and form bands, leading to rather complicated Fermi surfaces. The exchangeinteraction known as Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between the localised 4f
moments is mediated by these delocalised electrons. It is long-ranged and results in the oscillatory
behaviour of the magnetic coupling as a function of the separation between the atoms [3],described by the electron wavevectors at the Fermi surface. In a periodic lattice this causes
certain frustrations and results in several magnetic phases, from simple ferromagnetism to
antiferromagnetic helical [2,4]. When the system size is reduced, electronic wavefunctions
mediating the exchange are constrained by the boundaries. Because of this, surfaces often show
magnetic properties drastically different from the bulk [5]. The behavior becomes even more
extreme if the size of the whole system is comparable to the length scale of the bulk exchange.
Here we follow, both experimentally and theoretically, the development of magnetism in Tb
clusters from the atomic limit and adding one atom at a time. The exchange is, surprisingly, shown
to drastically increase compared to that of the bulk, and to oscillate as a function of the interatomic
distance. Unlike the bulk, the oscillation is not caused by the RKKY mechanism. Instead, theexchange is shown to be driven by finite size effects, leading to the variations of the exchange
between ferromagnetic double-exchange and antiferromagnetic super-exchange mechanisms. As
a consequence, the magnetic moment oscillates with cluster size in exact agreement withexperimental data. Therefore the finite size effects and quantum confinement are key parameterswhen designing new rare-earth based magnets.
Reference(s)[1] A. Delin, L. Fast, B. Johansson, J.M. Wills, O. Eriksson, Phys. Rev. Lett. 79 (1997) 4637
[2] J. Jensen and A.R. Mackintosh, Rare Earth Magnetism (Clarendon Press, Oxford, 1991)[3] D.A. Goodings, J. Phys. C (Proc. Phys. Soc.), ser. 2, vol. 1 (1968) 125[4] L. Nordström and A. Mavromaras, Europhys. Lett. 49 (2000) 775[5] E. Vescovo, C. Carbone, and O. Rader, Phys. Rev. B 48 (1993) 7731.

Electron correlation: magnetism and superconductivity

B3

Relation between valence of iron ions in maghemite nanoparticles and theirsaturation magnetization
Keita Kobayashi,1 Kazunari Nojiri,2 Tomoyuki Terai,2 Tomoyuki Kakeshita2 and Hidehiro Yasuda1,2
1Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, Ibaraki, Osaka
567-0047, Japan
2

Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka
University, Suita, Osaka 565-0871, Japan

Since solid state properties of nanomaterials strongly depend on the size, to understand detailed
mechanism of size dependence of the properties is important for practical application of novel
nanomaterials. Especially, clarification of mechanism of size dependency of magnetic properties
has been required because nano magnetic materials have been expected as key materials fordevelopment of high density storage media and medical applications.
In this study, to clarify the mechanism of diameter dependence of magnetic properties of magnetic
nanomaterials, maghemite (γ-Fe2O3) nanoprticles with various diameter distributions wereprepared by coprecipitation, and the saturation magnetization and the microscopic structures andelectronic states of these nanoparticles were compared by vibrating sample magnetometry,transmission electron microscopy, and electron energy loss spectroscopy.
Although transmission electron diffractometry did not reveal any structural differences between
nanoparticles, we found, by electron energy loss spectroscopy, that the valence of iron ion in thenanoparticles tended to change from Fe3+ to Fe2+ with decreasing the saturation magnetization.
These results suggest that the decreasing saturation magnetization is attributed to increase ofoxygen deficiency density in the nanoparticles.
This work was supported by KAKENHI (#25790003) from JSPS. The authors thank Mr. M. Fujisaki(Renovation Center of Instruments for Science Education and Technology, Osaka University) for
ICP measurements, and Hayashibara Co., Ltd. for providing a portion of reagent used in thisstudy.

Electron correlation: magnetism and superconductivity

B4

Magnetization and Mössbauer Study of Partially Oxidized Iron cluster Films
Deposited on HOPG
Nils Tarras-Wahlberg1, Saeed Kamali2, Mats Andersson1,3, Christer Johansson4, and Arne
Rosen1,5
1Experimental Physics, Gothenburg University and Chalmers University of Technology, SE-412
96, Göteborg, Sweden
2

3

Department of Chemistry, University of California, Davis, California 95616, USA

Department of Applied Mechanics, Chalmers University of Technology, SE-412 96, Göteborg,
Sweden4

Acreo Swedich ICT AB, Arvid Hedvalls Backe 4, SE-400 14, Göteborg, Sweden

5

Department of Physics, Gothenburg University, SE-412 96 , Göteborg, Sweden

Iron clusters produced in a laser vaporization source were deposited to form cluster-assembled
thin films with different thicknesses on highly oriented pyrolytic graphite substrates. The
development of oxidation of the clusters with time, up to three years, was investigated by magnetic
measurements using an alternating gradient magnetometer [1]. Furthermore, to receive
information about the oxidation states, clusters of 57Fe were studied using Mössbauer
spectroscopy. The magnetic analysis shows a time evolution of the saturation magnetization,
remanence, and coercivity, determined from the hysteresis curves characteristic of a progressing
oxidation. The different thicknesses of the iron cluster films as well as a protective layer of
vanadium influence the magnetic properties when the samples are subjected to oxidation withtime. While the saturation magnetization and remanence decrease and reach half the initial values
for almost all the samples after three years, the coercivity increases for all samples and is more
substantial for the thickest sample with a vanadium protective layer. This value is three folded after
three years. Furthermore, based on a core-shell model and using the saturation magnetization
values we have been able to quantitatively calculate the amount of the increase of Fe-oxide as afunction of time. The Mössbauer spectroscopy shows peaks corresponding to iron metal andmaghemite.
Reference(s)[1] N. Tarras-Wahlberg, S. Kamali, M. Andersson, C. Johansson, A. Rosén,
Journal of Magnetism and Magnetic Materials 367, 40 (2014)

Electron correlation: magnetism and superconductivity

B5

Term rules for small aluminum clusters
Daisuke Yoshida, Hannes Raebiger
Department of Physics, Yokohama National University, Yokohama, JapanThe ground states terms of isolated atoms are determined by Hund’s rules, which are explained by
the lowering of the electronuclear attraction energy [1-3]. For molecules and clusters, such term
rules do not exist. We search for such terms rules by first principles calculation of small Al clusters.
Bulk Al is paramagnetic, but in low dimensional structures Al atoms may spontaneously align theirspins. Aln clusters with even n = 2, 4, 6,8 have spin-triplet ground states [3-6]. Al3 on the other
hand has spin-doublet (low spin) state and spin-quadruplet (high spin) configurations, but which
one of these is the ground state remains unsolved [7-10]. Our present benchmark study confirmsthat Al dimer has the 3 Pu high spin ground state and unambiguously shows that Al trimer has the2

A'1 low spin ground state. Al dimer is consistent with both Hund’s first and second rules, but the

ground state term cannot be explained by traditional interpretations [1-4,11-13]. Al trimer violates
Hund’s rule. Al dimer’s high spin term is stabilized by Fermi correlation, whereas Al trimer’s low
spin is stabilized by Coulomb correlation which overwhelms Fermi correlation. We show that all
the molecular terms of dimer and trimer can be described by simple rules pertaining to bonding
structures and symmetries. This mechanism is described by our high accuracy variational
calculation.
References[1] J. Katriel and R. Pauncz, Adv. in Quantum Chem. 10, 143 (1977).
[2] R. J. Boyd, Nature 310, 480 (1984).
[3] T. Oyamada, K. Hongo, Y. Kawazoe, and H. Yasuhara, J. Chem. Phys. 133, 164113 (2010).
[4] G. Pacchioni, D. Plavˇsić, and J. Koutecký, Ber. Bunsenges. Phys. Chem. 87, 503 (1983).
[5] L. Pettersson, C. W. Bauschlicher, and T. Halicioglu, J. Chem. Phys. 87, 2205 (1987).
[6] C. W. Bauschlicher, H. Partridge, S. R. Langhoff, P. R. Taylor, and S. P. Walch, J. Chem. Phys.
86, 7007 (1987).
[7] D. M. Cox, D. J. Trevor, R. L. Whetten, E. A. Rohlfing, and A. Kaldor, J. Chem. Phys. 84, 4651
(1986).
[8] J. A. Howard, R. Sutcliffe, J. S. Tse, H. Dahmane, and B. Mile, J. Phys. Chem. 89, 3595 (1985).
[9] J. Tse, J. Chem. Phys. 92, 2488 (1990).
[10] Y. M. Hamrick, R. J. Vanzee, and W. Weltner, J. Chem. Phys. 96, 1767 (1992).
[11] J. C. Slater, Phys. Rev. 34, 1293 (1929).
[12] J. H. Van Vleck, J. Chem. Phys. 3, 807 (1935).
[13] J. P. Colpa and R. E. Brown, J. Chem. Phys. 68, 4248 (1978).

Electron correlation: magnetism and superconductivity

B6

Self-doping of ultrathin insulating films by transition metal atoms
Z. Li,1,* H.-Y. T. Chen,2 K. Schouteden,1 L. Giordano,2 M. I. Trioni,3 E. Janssens,1
V. Iancu,1 C. Van Haesendonck,1 P. Lievens,1 and G. Pacchioni2

1

Laboratory of Solid-State Physics and Magnetism, KU Leuven, BE-3001 Leuven, Belgium

2

Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, I-20125 Milano, Italy3

CNR - National Research Council of Italy, ISTM, I-20133 Milano, Italy

Deposition of metal atoms on solid surfaces is usually employed to study nucleation and growth ofmetal nanoparticles that are relevant for heterogeneous catalysis, sensors, optical and magnetic
data storage, etc. Growth of ultrathin films of insulating materials on a metallic substrate prior atom
deposition can provide additional control of the coupling of the metal adsorbates with the metallic
substrate [1–3]. Soft landing of metal atoms on insulating thin layers is typically noninvasive andresults in cluster growth with little or no surface damage.
Here, we demonstrate an uncommon case of spontaneous
doping by transition metals on ultrathin insulating films.
Individual magnetic atoms (Co and Cr) are deposited on
atomically thin NaCl films on Au(111). Two different adsorption
sites are revealed by high-resolution scanning tunnelingmicroscopy (STM), i.e., at Na and at Cl locations. Usingdensity functional based STM simulations, we show that themagnetic atoms substitute with either a Na or Cl atom of the
NaCl surface, resulting in cationic and anionic dopants with ahigh thermal stability. Moreover, since the dopants bear large localized magnetic moments, thedimers represent an ideal system to study magnetic interactions between diluted magnetic
impurities in an insulating matrix. By mapping the local density of states, the dependence of themagnetic coupling between neighboring magnetic atoms on their separation is investigated [4].
The here reported self-doping of an insulating material by magnetic atoms may open a novel routeto tune catalytic, optical, magnetic, and transport properties of materials.
Reference(s)[1] J. Repp, et al., Science 305 (2004) 493.
[2] J. Repp, et al., Phys. Rev. Lett. 95 (2005) 225503.
[3] C. F. Hirjibehedin, et al., Science 317 (2007) 1199.
[4] Z. Li, et al., Phys. Rev. Lett. 112 (2014) 026102.

Electron correlation: magnetism and superconductivity

withdraw

B7

Electron correlation: magnetism and superconductivity

B8

Probing the phonon density of states and its effect on superconductivity
in Sn nanoparticles, nano-islands, and cluster-assembled films
K. Houben1, S. Couet2, J. Jochum1, D. Pérez2, M. Bisht2, M.Trekels2, T. Picot1, R. Rüffer3,
M.Y. Hu4, S.A. Brown5, F.M. Peeters6, P. Lievens1, A. Vantomme2, K. Temst2, M.J. Van Bael1
1

Laboratory of Solid-State Physics and Magnetism, KU Leuven, Belgium
2
3

4
5

Instituut voor Kern- en Stralingsfysica, KU Leuven, Belgium

European Synchrotron Radiation Facility (ESRF), Grenoble, France

Advanced Photon Source (APS), Argonne National Laboratory, Illinois USA

MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury, NZ
6Departement Fysica, Universiteit Antwerpen, Belgium

Phonons influence many material properties, such as thermal and mechanical behavior.
Furthermore, the electron-phonon interaction lies at the basis of Cooper-pair formation and istherefore of crucial importance in conventional phonon-mediated superconductivity. As worked out
in the Eliashberg formalism, the phonon density of states (PDOS) directly determines key
superconducting parameters such as the electron-phonon coupling strength and the criticaltemperature TC. When reducing the system dimensions down to the nanometer scale, phonon
confinement effects and the appearance of surface phonon modes result in deviations in thephonon density of states with respect to the corresponding bulk PDOS [1]. Such phonon
confinement effects may in turn induce changes of the superconducting properties [2]. While thephonon spectrum of bulk systems is well understood, considerably less is known about thevibrational behavior in nanostructures because of the difficulty of experimentally probing atomic
vibrations at this scale.
Tin (Sn) is known as a weak-coupling superconductor with a bulk TC of 3.72 K. Significant TC
enhancements have been observed in weak-coupling superconducting nanostructures [3], whichare (partially) ascribed to confinement effects of the phonon spectrum. In this work, we haveexperimentally measured the PDOS of embedded Sn nanoparticles in SiO2, Sn cluster-assembled
layers and Sn nano-islands by nuclear inelastic scattering (NIS) of synchrotron radiation which
specifically probes the 119Sn isotope [2]. The PDOS of all these nanoscale Sn systems show clear
modifications compared to that of a reference bulk Sn sample, such as an energy redistribution of
the phonon modes or the appearance of new modes. Moreover, TC enhancements well above
10% were detected in the superconducting properties and we have disentangled to what extent
this is attributable to the observed phonon confinement effects. For the thicker Sn islands, we canconclude that phonon confinement does explain the modified TC, while for the smaller islands andcluster-assembled Sn films other effects like electron confinement become more important.
Reference(s)[1] B. Roldan Cuenya et al., Phys. Rev. B 64 (2001) 235321.
[2] S. Couet et al., Phys. Rev. B 88 (2013) 045437.
[3] B. Abeles et al., Phys. Rev. Lett. 17 (1966) 632.

Electron correlation: magnetism and superconductivity

B9

X-ray absorption spectroscopy of free, size selected, singly metal doped
silicon clusters
Vicente Zamudio-Bayer1,2, Linn Leppert3, Konstantin Hirsch2,4, Arkadiusz Ławicki2,
Andreas Langenberg2,4, Jochen Rittmann2,4, Martin Kossick2,4,
Marlene Vogel2,4, Robert Richter2,4, Thomas Möller4, Akira Terasaki5,6,
Stephan Kümmel3, Bernd von Issendorff1 and Julian Tobias Lau2
1

Fakultät für Physik, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg, Germany
2

Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung,Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489
Berlin, Germany
3

Theoretische Physik IV, Universität Bayreuth, 95440 Bayreuth, Germany
4

Institut für Optik und Atomare Physik, Technische Universität Berlin,
Hardenbergstraße 36, 10623 Berlin, Germany
5

Cluster Research Laboratory, Toyota Technological Institute,717-86 Futamata, Ichikawa, Chiba 272-0001, Japan

6

Department of Chemistry, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581,
Japan

The size dependent magnetic properties and electronic structure of small, 3d transition metal
doped silicon clusters have been studied spectroscopically. The cluster ions were size selected,
stored in a liquid Helium cooled ion trap and irradiated with the x-ray beam from an undulator at
the BESSY II synchrotron facility. The x-ray absorption and x-ray magnetic circular dichroism(XMCD) at the L2,3-edges of the single 3d transition metal impurity were measured in ion yieldmode [1]. Special emphasis was placed on the influence that the encapsulation of the single
impurity at the exo- to endohedral doping transition has on the magnetic moment. Information on
the geometries of the clusters was obtained by combining the experimental results with density
functional theory calculations. By applying the XMCD sum rules [2], it was furthermore possible toresolve the spin and orbital contribution to the impurity’s magnetic moment as a function of thecluster’s chemical composition and geometry. The correlation of magnetic moment with dopant
coordination and metal silicon nearest-neighbor distance observed in this model systems can begeneralized to bulk dilute magnetic semiconductors.
Reference(s)[1] V. Zamudio-Bayer, L. Leppert, K. Hirsch, A. Langenberg, J. Rittmann, M. Kossick, M. Vogel,
R. Richter, A. Terasaki, T. Möller, B. v. Issendorff, S. Kümmel, and J. T. Lau, Phys. Rev. B, 88,
115425 (2013)[2] B. T. Thole, P. Carra, F. Sette, and G. van der Laan, Phys. Rev. Lett., 68, 1943 (1992);
P. Carra, B. T. Thole, M. Altarelli, and X. Wang, Phys. Rev. Lett., 70, 694 (1993)

Electron correlation: magnetism and superconductivity

B10

Magnetic moments of chromium-doped gold clusters: The Anderson impurity
model in finite systems
K. Hirsch1, 2, V. Zamudio-Bayer5, A. Langenberg1, 2, M. Niemeyer1, 2, B. Langbehn1, 2, T. Möller2,
A. Terasaki3, 4, B. v. Issendorff5 and J. T. Lau1
1

Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung,Helmholtz-Zentrum Berlin für Materialien und Energie GmbH,
Albert-Einstein-Straße 15, 12489 Berlin, Germany

2

Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstraße 36,10623 Berlin, Germany
3

Cluster Research Laboratory, Toyota Technological Institute,717-86 Futamata, Ichikawa, Chiba 272-0001, Japan

4

Department of Chemistry, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581,
Japan
5

Fakultät für Physik, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg, Germany

A long standing problem in condensed matter physics is the interaction of a single magnetic
impurity with a free electron gas resulting in interesting many body phenomena like the Kondo
effect. In recent years substantial progress was obtained by pushing the experiments to atomic
scales. Here we want to follow this approach and investigate the interaction of a single magnetic
impurity with a finite free electron gas. CrAun+ clusters serve as a model system [1]: We can showthat the size dependence of the local spin magnetic moment of CrAun+ clusters can be welldescribed within a modified version of the Anderson impurity model taking into account the highly
discretized density of states of the gas phase gold host [2,3]. The interaction of the localized
impurity states with the electron bath of the gold matrix is governed by quantum confinement in thehost. We show that the size of the impurity spin magnetic moment can be controlled by the size ofthe energy gap in the host density of states. This introduces the possibility to even restore the spin
degree of freedom of the impurity atom although absent in the corresponding bulk material.
Reference(s)[1] K. Hirsch et al., submitted to Phys. Rev. Lett.
[2] P. W. Anderson, Phys. Rev. 124, 41 (1961).
[3] K. Hirsch et al., submitted to Phys. Rev. B

Electron correlation: magnetism and superconductivity

B11

Superconducting properties of nanoparticles and small clusters
T. Picot1, H. Wang2, K. Houben1, A. Hillion1, S. Bals3, S.A. Brown4, E. Janssens1, P. Lievens1, A.
Vantomme2, K. Temst2, M.J. Van Bael1
1

Laboratory of Solid-State Physics and Magnetism, KU Leuven
2

3
4Instituut voor Kern- en Stralingsfysica, KU Leuven

Elektronenmicroscopie voor Materiaalonderzoek, Universiteit Antwerpen

The MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Canterbury

We present two different approaches to study the superconducting properties of small particles
with a size ranging from a few nanometers down to the sub-nanometer scale with clusters made ofa countable number of atoms. In the first approach, ion implantation has been used to synthesize
Pb nanoparticles with a diameter ranging from 8 to 20 nm inside an Al matrix [1]. Detailled

structural characterization of the nanocomposite material shows the highly epitaxial relation
between the nanoparticles and the crystalline matrix. The Al/Pb nanocomposites display asingle superconducting transition temperature increasing linearly with the amount of Pb. Our
experimental data can be well described by superconducting proximity effect models for strongly
coupled superconductors with a value of the electron-phonon coupling constant for the Pb
nanoparticles of λ = 1.2 slightly lower than in bulk Pb (λ = 1.55). Our analysis reveals the highquality of the matrix-nanoparticle interface obtained by ion implantation synthesis. In the second
approach, nanoparticles and small clusters are produced using a magnetron sputtering cluster
source equipped with a high resolution RF quadrupole mass filter and a UHV deposition chambercompatible with in situ STM. We give a general overview of the source and the cluster size
distribution in different production regimes. Perspectives are discussed to study thesuperconducting properties of small size-selected deposited clusters.
Reference(s)[1] H. Wang et al. Supercond. Sci. Technol. 27 (2014) 015008

Energy-related topics & Environmental studies

B12

Formic Acid Oxidation Catalytic Properties of Pd Nanoparticles Prepared by
Physical Vapor Deposition
L.S. Wang a, M. Lei, J.B. Wang, C.Y. Zou and D.L. Peng b
Department of Materials Science and Engineering, College of Materials, Xiamen University,
Xiamen 361005, P. R. China
Corresponding authors: a wangls@xmu.edu.cn; b pengdl@xmu.edu.cn
Pd catalysts in nanoscale showed better catalysis efficiency for formic acid oxidation, and hold agreat potential to replace Pt due to its lower cost and more resistance to CO poisoning.[1] However,traditional chemosynthesis has been a long standing challenge in obtaining Pd nanoparticles withultraclean surface. Fortunately, these problems are expected to be resolved by physical vapor
deposition which is different from traditional chemosynthesis. [2]In this work, Pd nanoparticles were synthesized under the high vacuum and inert gas condition byusing the plasma-gas-condensation clusters deposition apparatus (see Fig.1), and softly landedon the glassy carbon plate (GCP) directly. The Pd cluster-assembled films whose packing density
was only about 30% for bulk Pd were obtained. The Pd catalysts prepared here have many
advantages including ultraclean surface, small size and porous stacks which can achieve more
active sites, larger specific surface area and effective contact area in catalytic reaction, therefore,
the excellent electrocatalytic activities including a large electrochemical surface area (100.0 m2 g-1),
a high current density peak of formic acid oxidation (0.58 mA cm -2 and 0.55 mA μg-1Pd) andconsiderable stability have been obtained. Furthermore, the effects of substrate temperatures on
catalytic activity have been studied.
Based on what we have discussed above, we supposed that our recent research would focus wide
interests among chemists and material scientists, and desirable to share with other researchers assoon as possible. Further investigation is carrying out in in our laboratory currently.

Fig. 1. Schematic diagram of Pd NC deposition process in the nanoparticle composite deposition system.

Reference(s)[1] V. Mazumder, M. Chi, M. N. Mankin, Y. Liu et al., Nano letters 12 (2012) 1102-1106.
[2] L.S. Wang, R.T Wen, Y. Chen, D.L. Peng, T. Hihara, Appl. Phys. A 103 (2011) 1015-1020.

Energy-related topics & Environmental studies

B13

Fabrication of Si nanoparticles from Si swarf
and the application to hydrogen generation source
Taketoshi Matsumoto,1 Katsuya Kimura,1 Kentaro Imamura,1 Masao Takahashi,1 Yayoi Kanatani2
Tohru Higo,2 and Hikaru Kobayashi2
1

ISIR, Osaka University and CREST-JST, Ibaraki, Japan

2

Nisshin Kasei Co., Ltd. and CREST-JST, Osaka, Japan

Si nanoparticles have a potential for a hydrogen generation source [1]. We have developed afabrication method of Si nanoparticles from Si swarf applicable to light emitting materials [2] andsolar cells [3]. Si swarf is an industrial waste generated during slicing Si ingots for fabrication ofsolar cells and LSI, and thus, the production cost for Si nanoparticles can be reduced remarkably
by use of Si swarf. In this study, the Si nanoparticles are produced from Si swarf and the reaction
mechanism with water to generate hydrogen is investigated.
Si swarf was milled with a beads mill to fabricate Si nanoparticles. X-ray diffraction patterns
showed clear peaks assigned to crystalline Si.

The volume distribution of Si nanoparticles

evaluated using the algorism proposed by Ida et al.[4] showed the maximum distribution diameterof 6.1 nm. An SiO2 layer on Si nanoparticles was etched in 50wt% HF aqueous solutions,followed by rinse with ultrapure water. Si nanoparticles were immersed in 40wt% HNO3 to form
ultrathin SiO2 layer to prevent Si nanoparticles from floating on the solutions.
Si nanoparticles were immersed in 100 ml water of pH controlled with KOH. The hydrogengeneration rate for the initial 2.5 min reached to ~400 ml/min.g at 50°C and pH of 13, i.e., 1000 mlhydrogen was produced from 1 g Si nanoparticles in 2.5 min. The hydrogen generation stopped
when ~1100 ml/g hydrogen was generated due to formation of an SiO2 layer on the Si
nanoparticle surface as indicated by X-ray photoelectron spectra. By removal of the SiO2 layer
with HF solutions, ~500 ml/g hydrogen was generated again to from these Si nanoparticles. The
hydrogen generation rate and also the total evolved hydrogen volume decreased by a decrease in
pH of the solutions. It is concluded that in the case of high pH, the Si dissolution reaction is
predominant while the reaction for SiO2 formation on Si nanoparticle surface is dominant for low
pH.
References[1] F. Erogbogbo, T. Lin, P.M. Tucciarone, K.M. LaJoie, L. Lai, G.D. Patki, P.N. Prasad, and M.T.
Swihart, Nano Lett. 13 (2013) 451.
[2] T. Matsumoto, M. Maeda, J. Furukawa, W.-B. Kim, and H. Kobayashi, J. Nanopart. Res. 16(2014) 2240.
[3] M. Maeda, K. Imamura, T. Matsumoto, and H. Kobayashi, Appl. Surf. Sci. in press.
[4] T. Ida, S. Shimazaki, H. Hibino, H. Toraya, J. Appl. Crystal. 36 (2006) 1107.

Energy-related topics & Environmental studies

B14

Structural and optical properties of “Cauliflower” silicon nanoparticles
Wingjohn Tang1, Joren Eilers2, Marijn van Huis1, Da Wang1, Ruud Schropp3, Andries Meijerink2,
Alfons van Blaaderen1, Marcel Di Vece1 41Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University,
Princetonplein 5, 3584 CC Utrecht, The Netherlands

2Condensed Matter and Interfaces, Debye Institute for Nanomaterials Science, Utrecht University,
Princetonplein 5, 3584 CC Utrecht, The Netherlands

3

Energy research Center of the Netherlands (ECN), Solar Energy, High Tech Campus Building 5,5656 AE Eindhoven; and Eindhoven University of Technology (TU/e), Department of Applied
Physics, Plasma & Materials Processing, P.O. Box 513, 5600 MB Eindhoven
4

Nanophotonics—Physics of Devices, Debye Institute for Nanomaterials Science, Utrecht
University, P.O. Box 80000, 3508 TA Utrecht, The Netherlands

The photovoltaics (PV) market is currently dominated by silicon based solar cell technology
because of its relative ease of production and its consistence of abundant and non-toxic materials
only. Although new concepts and materials are intensively investigated to increase efficiencies
even more, silicon remains a very attractive PV material. Combining silicon with one of such newconcepts, the quantum dot, may lead to enhanced device performance[1]. The advantage ofsilicon quantum dots are their tunable band gap, which can be employed in a tandem cell, and the
direct optical transition, which increases absorption.
In this work we produced silicon nanoparticles with a gas aggregation cluster source by magnetron
sputtering. The silicon particles were deposited on a substrate and investigated with a suit oftechniques such as transmission electron microscopy (TEM), Raman spectroscopy and (timeresolved) photoluminescence spectroscopy. Various stages of silicon nanoparticle formation wereidentified, depending on the cluster source operational parameters. ‘Cauliflower’-like particles ofabout 50-100 nm exhibited the most interesting optical features. They are likely formed byaggregation of smaller silicon nanoparticles and are an intermediate state towards large crystalline
particles. These ‘cauliflower’ silicon particles contain pockets of crystalline and amorphous silicon(a-Si). In agreement with the direct bad gap of a-Si, a photoluminescence signal belonging to thisstate was measured [2]. Although the dimensions of the a-Si pockets are small, no quantum
confinement effects could be observed, likely due to the very close proximity of neighbouring
particles. In this study we explored the optical and structural properties of ‘cauliflower’ silicon
nanoparticles, which forms a diving board to using cluster source produced silicon particles for PV.
Reference(s)[1] G. Conibeer, Mat. Today, 10, 42 (2007)[2] A. Vivas Hernandez et al. J. of Physics: Conf. Series 61,1233 (2007)

Energy-related topics & Environmental studies

B15

Sulfuric acid clusters in atmospheric particle formation:
insights from computational approaches
Henning Henschel,1 Oona Kupiainen-Määttä,1 Theo Kurtén,2 Ville Loukonen,1 Tinja Olenius,1 andHanna Vehkamäki1
1
2

Department of Physics, University of Helsinki, Helsinki, Finland

Department of Chemistry, University of Helsinki, Helsinki, Finland

A significant fraction of atmospheric aerosol particles are formed in the atmosphere from condensable vapors. The phenomenon is often initiated by sulfuric acid, with the most likely other key
participants in the lower troposphere being ammonia, amines and other organic compounds. Thevery first steps of the process involving the formation of stable clusters are among the most challenging to approach, both theoretically and experimentally. Earlier theories based on macroscopic
thermodynamics have failed to reproduce experimental particle formation rates; at present, molecular-level computational chemistry and physics are the state-of-the-art tools to study atmospheric clustering processes, and have produced thus far the best agreement with observations.
The palette of computational methods ranges from electronic structure calculations and molecular
dynamics simulations to kinetic cluster population models. While static minimum-energy calculations may reveal the general trends in cluster stability, first-principles molecular dynamics simulations describe the atomic-level movement in a complex of molecules and dynamics related to collisions and cluster rearrangement [1]. To study a larger population of clusters interacting with eachother, cluster free energies from electronic structure calculations can be converted into evaporation rates and incorporated into kinetic models [2]. This provides a means to assess the formation
rate of clusters of a specific size in given conditions, but also a possibility for a direct comparison
with experiments through mass spectrometer measurements of cluster distributions. While thedescription of collision and evaporation processes in this type of simulation is not as rigorous ascan be achieved with molecular dynamics, the approach reproduces observed trends [2], and canthus be used to predict the general behavior of a cluster population.
Our recent cluster kinetics simulations for clusters containing sulfuric acid, ammonia anddimethylamine provide information on the relative potential of the different bases to enhance sulfuric acid driven clustering. The effect of water in these systems is current work-in-progress. In
addition to cluster formation in the conditions of laboratory or field measurements, simulations canbe used to study the effect of measurement methods, such as chemical ionization [3].
References[1] V. Loukonen et al., Chem. Phys. 428 (2014) 164–174.
[2] J. Almeida et al., Nature 502 (2013) 359–363.
[3] O. Kupiainen-Määttä et al., J. Chem. Phys. A 117 (2013) 14109–14119.

Optical properties and plasmonics

B16

Photoluminescence properties of Si nanoparticles fabricated from Si swarf:
fluorescence enhancement by organic molecules
Masanori Maeda, Taketoshi Matsumoto, and Hikaru Kobayashi
The Institute of Scientific and Industrial Research, Osaka University
and CREST, Japan Science and Technology Agency, Ibaraki, Japan
Light emitting Si nanoparticles have attracted much interest because of their unique andapplicative characteristics (e.g., controllability of emission wavelength, biocompatibility andsurface sensitivity) [1]. We have developed a method of fabricating blue light emitting Si
nanoparticles from Si swarf, which is a waste generated during slicing Si ingots to produce Siwafers for solar cell use [2]. In this study, we have produced blue and green light luminescent Si
nanoparticles by use of a simple method, and observed their fluorescence enhancement effect ofadsorbed organic molecules. Si swarf generated by use of the fixed-abrasive method was milled
by use of a beads mill. After milling, transmission electron microscope (TEM) and X-ray diffraction(XRD) observation clearly showed the presence of many Si nanoparticles with diameters less than
10 nm. Si nanoparticles etched with HF solutions exhibited green photoluminescence (PL) under
UV irradiation. The PL peak clearly showed blue shifts by an increase in the excitation energy.
This result indicates that the green PL originates from band-to-band transition of Si nanoparticles
with the quantum confinement effect. After filtering and extracting by 9,10-dimethylanthracene(DMA) containing hexane plus water without HF etching, on the other hand, Si nanoparticles
showed strong blue PL. The PL spectra of blue PL Si nanoparticles have no dependence on the
excitation energy. In addition, the spectral feature is very similar to that of DMA. Therefore, it canbe concluded that blue PL arises from DMA molecules adsorbed on Si nanoparticles. The PL
intensity is much higher than that of DMA-containing hexane. The increased PL intensity is
attributed to enhancement of UV absorption by Si nanoparticles, followed by transfer ofelectron-hole pairs to DMA and recombination there. From these results, we propose two different
methods to control the PL wavelength; 1) control of the size of Si nanoparticles, and 2) control ofadsorbed species on Si nanoparticles.
References[1] Z. Kang, Y. Liu, and S-T. Lee, Nanoscale 3 (2011) 777-791.
[2] T. Matsumoto, M. Maeda, J. Furukawa, W-.B. Kim, and H. Kobayashi, J. Nanopart. Res. 16(2014) 2240-1-7.

Optical properties and plasmonics

B17

Ag44SR30: What comes after the structure is solved?
Lars Gell,1 Hannu Häkkinen1,2
1

Department of Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finland2

Department of Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finland

The crystal structure of Ag44SR304- has gained considerable attention since its simultaneous
publication by Zhen and Bigioni groups. Various modifications like different R groups, replacementof the inner silver core with gold as well as sulfur with selenium have already been discovered.
[1,2,3] In this study we will discuss the influence of cluster charge and electron withdrawing
ligands on the optical absorption spectra as well as the plasmonic nature of this nanoparticle. We
show that the cluster can bind up to four protons reducing its high charge of four minus to zero.
Furthermore the possibility of producing magnetic nanoclusters upon doping with manganese
will be discussed.

Figure1: The plasmon like nature of Ag44SR304- upon excitation around 400 nm is shown. The
counter interacting field of the silver-d states (right) and ligand+silver-s states (left) can be seenfrom the induced density as well as the contribution of the phenyl rings to the plasmonic peak.
Reference(s)[1] H. Yang, Y. Wang, H. Huaqi, L. Gell, L. Lehtovaara, S. Malola, H. Häkkinen and N. Zheng, Nat.
Comm. 2013, 4-2422[2] I. Chakraborty, W. Kurashige, K. Kanehira, L. Gell, H. Häkkinen, Y. Negishi and T. Pradeep.
Phys. Chem. Lett. 2013, 4, 3351
[3] A. Desireddy, B.E. Conn, J. Gou, B. Yoon, R. N. Barnett, B. M. Monahan, K. Kirschbaum, W. P.
Griffith, R. L. Whetten, U. Landman, T. P. Bigioni, Nature, 2013, 501, 399

Optical properties and plasmonics

B18

Information on Quantum States Pervades
the Absorption Spectra of the Au144 (SR)60 Nanocluster
H.-Ch. Weissker1,2, V.D. Thanthirige4, K. Kwak5, D. Lee5,
G. Ramakrishna4, R.L. Whetten3, X. López-Lozano3
1

Aix-Marseille Univ., CNRS, CINaM UMR 7325, 13288 Marseille, France.
2

3

European Theoretical Spectroscopy Facility, France; www.etsf.eu.

Department of Physics and Astronomy, The University of Texas at San Antonio. One UTSA
Circle, San Antonio, Texas 78249, USA.
4

Department of Chemistry, Western Michigan University, 1903 West Michigan Avenue,
49008-5413 Kalamazoo, Michigan, USA.
5

Department of Chemistry, Yonsei University, Seoul 120-749, Korea.

The prevalent view in recent decades has been that noble-metal clusters of intermediate size
necessarily have smooth optical absorption spectra of low information content in the near-IR, VIS
and near-UV regions. At most, one expects a broad, smooth localized surface-plasmon resonancefeature. 1,2 In the present study, we demonstrate that, in contradistinction to the commonly heldview, the optical absorption of the most widely applied gold cluster, the thiolate-protected Au144(SR)60, exhibits a rich spectrum of bands that are individually visible over the entire near-IR, VIS
and near-UV regions (1.0–4.0 eV), demonstrating high information content related to the quantum
size effects which distinguish the nanoparticles from the bulk materials.3 The contributions ofdifferent parts of the cluster-ligand compound to the spectra are analyzed. The results wereobtained owing to low-temperature measurements on ultrahomogeneous samples and realistic
quantum-theoretical simulation (~2,500 active electrons) using time-dependent density-functional
theory. 4-6
References[1] Qian, H., Zhu, Y. & Jin, R., Proc. Natl Acad. Sci. USA 109, 696–700 (2012).
[2] Malola, S., et al., ACS Nano. 7, 10263–10270 (2013).
[3] de Heer, W. A., Rev. Mod. Phys. 65, 611–676 (1993).
[4] López-Lozano, X.; Mottet, C.; Weissker, H.-Ch.; J. Phys. Chem. C, 117, 3062–3068 (2013).
[5] López-Lozano, X.; Barron, H.; Mottet, C.; Weissker, H.-Ch., Phys. Chem. Chem. Phys. 16,
1820–1823 (2014).
[6] Weissker H.-Ch., et al., Nature Communications, 5, 3785, (2014).

B19

Optical properties and plasmonics

Preparation of non-toxic gold submicron-sized particles using laser-induced
melting in liquids
Takeshi Tsuji1, Yuuma Higashi2, Masaharu Tsuji2, Yoshie Ishikawa3, Naoto Koshizaki3
1

Interdisciplinary Faculty of Science and Engineering, Shimane University, Matuse, Japan
2

Institute of Advanced Materials Chemistry, Kyushu University, Kasuga, Japan

3

National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan
4

Faculty of Engineering, Hokkaido University, Sapporo, Japan

Recently, laser processes in liquid phase, such as laser ablation in liquids, attract much attention
as alternative methods to prepare colloidal materials. A remarkable benefit of laser processes isthat the use of undesirable reagents in the synthesis process can be minimized. The laser-induced
melting in liquids method, in which colloidal nanoparticles (NPs) are irradiated by non-focusedlaser beam at moderate fluence, is a novel and conventional technique to prepare sphericalsubmicron-sized particles (SSMPs) with narrow size distribution.

In the previous report, werevealed that control of the agglomeration conditions of the source Au NPs is important to obtain
Au SSMPs efficiently [1]. Therefore, in the previous study, tri-sodium citrate was used as astabilizing reagent. In the present work, NaCl, is employed as a stabilizing reagent to prepare“non-toxic” gold SSMPs. Differing from citrate, NaCl is not decomposed and no unnecessary
byproduct is formed by laser irradiation.
The source NPs were prepared by using laser ablation of a Au plate immersed in a NaCl aqueous
solution. It was confirmed that the stabilization of the source NPs was increased with increasing
concentration of NaCl [2]. The non-focused laser beamat 532 nm of a Nd:YAG laser was used to induce
melting of the source NPs.
Fig. 1 shows the SSMPs produced from the source
NPs in a 0.05 mM NaCl solution. SSMPs was notproduced from the source NPs in a 0.1 mM NaClsolution. This result shows that NaCl can be used tocontrol the agglomeration conditions of the source NPs.
On the other hand, it has been revealed that thedifference in the protective effect for the source gold
NPs between NaCl and citrate significantly influenceson the formation process of SSMPs.

Fig. 1 Au SSMPs produced by thelaser-induced melting of the source
Au NPs stabilized by 0.05 mM NaCl.

References[1] T. Tsuji, T. Yahata, M. Yasutomo, K. Igawa, M. Tsuji, Y. Ishikawa, N. Koshizaki, PCCP, 15(2013) 3099.
[2] J.P. Sylvestre, S. Poulin, A.V. Kabashin, E. Sacher, M. Meunier, J.H.T. Luong, J. Phys. Chem.
B, 108 (2004) 16864.

Optical properties and plasmonics

B20

Polymer-protected fluorescent platinum nanoclusters and their application
Xin Huang,1 Hidekazu Ishitobi,1, 2 and Yasushi Inouye1, 2, 3
1

Graduate School of Frontier Biosciences, Osaka University, 1-3 Yamada-oka, Suita, Osaka
565-0871, Japan2

Department of Applied Physics, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871,
Japan
3

Photonics Advanced Research Center, Osaka University, 2-1 Yamada-oka, Suita, Osaka
565-0871, Japan

Noble metal nanoclusters (M NCs) consisting of a few to several tens of atoms exhibit
molecule-like behaviors such as size-dependent fluorescence of which the emission wavelengths
can be adjusted by controlling the number of atoms in M NCs. Compared to common fluorophores,
M NCs have plenty of merits, such as water solubility, ultra-small size, and easy surface
modification. Recently, fluorescent gold and silver nanoclusters (Au NCs and Ag NCs) have been
already prepared and used for labeling the living cells as probes, while the fluorescent propertiesof the platinum nanoclusters (Pt NCs) are rarely discussed. In this presentation, we demonstrate
three kinds of different-colored (blue, green, and yellow-emitting) fluorescent Pt NCs. For blue andgreen-emitting Pt NCs, four-generation poly(amidoamine) dendrimers (PAMAM(G4-OH)) were
employed as a template.[1-2] Then we removed PAMAM dentrimers from the synthesized Pt NCs
via ligand exchange with thiol mercaptoacetic acid (MAA) after reduction. Since these Pt NCs
have the high quantum yield and considerably low cytotoxicity, they were successfully applied forbio-mark of chemokine receptors in the living HeLa cells by binding to an antibody through a
conjugated protein. On the other hand, the yellow-emitting fluorescent Pt NCs with excellent
photo-stability against both of pH and most metal ions were prepared by a facile method using
hyperbranched polyethyleneimine (PEI) as a stabilizing agent.[3] These fluorescent Pt NCs wereapplied to the sensitive and quantitative detection for Co2+ ions and the limit of detection was 500
nM. In future, fluorescent Pt NCs with longer-wavelength are expected to be produced by precise
control of the size.

References[1] S.-I. Tanaka, J. Miyazaki, D. K. Tiwari, T. Jin, and Y. Inouye, Angew. Chem. Int. Ed., 50,(2011) 431-435.
[2] S.-I. Tanaka, K. Aoki, A. Muratsugu, H. Ishitobi, T. Jin, and Y. Inouye, Opt. Mater. Express, 3,(2013) 157-165.
[3] X. Huang, K. Aoki, H. Ishitobi, and Y. Inouye, ChemPhysChem, 15, (2014) 642-646.

Optical properties and plasmonics

B21

Electrochemical Reactions and Spectral Changes of Gold-Silver Core-shell
Nanorods on ITO Plates
Yuki Hamsaki,1 Naotoshi Nakashima,1,,2,3 and Yasuro Niidome1,2,4
1

Department of Applied Chemistry, Kyushu University, Fukuoka, Japan
2

I2CNER WPI, Kyushu University, Fukuoka, Japan
3

4

CREST, Tokyo, Japan

Kagoshima University, Kagoshima, Japan (Present Affilication)

Au-Ag core-shell nanorods, of which spectroscopic properties corresponded to those ofanisotropic silver nanoparticles, are chemically unstable in the absence of reducing agent.
Oxidation of the silver shells gradually proceeded in an aqueous solution and accompanied bychanges in their shapes. In order to allow quantitative evaluation of the shape changes, a constantpotential electrolysis, to oxidize the silver shells, coupled with high resolution SEM analysis isherein performed. Oxidation processes of the silver shells in a KCl solution are discussed.
Well-controlled oxidation of silver shells is a potential way to give a new class of anisotropic
core-shell nanoparticles.
During electrolysis, the peak corresponding to the longitudinal SP band shifted to the shorter
wavelength region (Figure 1A). This shift indicated a decrease in the aspect ratios of thecore–shell nanorods. In a SEM image, oval nanoparticles and thin gold nanorods were observed.
The silver shells form water-soluble dichloride complexes (AgCl2-) that diffuse in the bulk solution,leaving core gold nanorods behind.
Figure 1B shows size distribution of the core-shell nanorods at 10 s after electrolysis in the KClsolution. The smaller portion of the bimodal size distribution is associated with the gold nanorods,
while the larger group corresponds
to the core–shell nanorods. The
distribution

indicates

core–shell

nanorods

that

the

remainanisotropic shapes even after the
10 s electrolysis. It should be
noted

that

there

are

a

few

spherical particles that are plotted on
the line indicating the aspect ratio isone. This indicated that oxidation ofsilver shells occurred at the cornersof the silver shells.

Fig. 1

Fig. 1. (A) Extinction spectral changes observed in thedeposited core–shell nanorods under an applied constant potential(0.15 V vs. SCE) in the KCl solution (0.1 M). (B) size distribution of
the deposited core–shell nanorods after a 10 s electrolysis. The scalebar indicates the frequencies of nanoparticles

Reference[1] Y. Hamasaki, N. Nakashima, Y. Niidome, J. Phys. Chem. C 117(2013)2521.

B22

Optical properties and plasmonics

Novel thiolate-protected gold clusters with sub-2 nm sized and fcc cores:
synthesis and optical property
Shinjiro Takano,1 Seiji Yamazoe,1,2 Kiichirou Koyasu,1,2 and Tatsuya Tsukuda1,2
1
2

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan[Metal clusters exhibit novel structures and properties that cannot be found in the corresponding
bulk metal. Thiolate-protected gold (Au:SR) clusters provide an ideal platforms to study the uniquegeometrical structures and electronic properties [1]. X-ray diffraction studies revealed that Au:SR
have Au cores with five-fold symmetry, such as icosahedron or decahedron, especially when theircore diameters are smaller than 2 nm. The Au:SR clusters (<2 nm) also have distinct opticalabsorption bands and exhibit luminescence, reflecting their quantized electronic structures. We
herein report the synthesis of new Au:SR clusters with sub-2 nm sized fcc cores and their novel
optical absorption bands in the near-IR region.
Small fcc Au:SR clusters were synthesized by a slow
reduction method. First, the aqueous-ethanolic solutions of
HAuCl4 and 4-(2-mercaptoethyl)benzoic acid (4-MEBA) weremixed. After the pH value of the mixed solution was adjusted
to be >12 by addition of KOH (sample 1) or NaOH (sample 2),
the aqueous solution of NaBH4 was added. Finally, pureAu:4-MEBA clusters were obtained as black powders after the
purification by gel filtration chromatography.
Powder XRD patterns of 1 and 2 (Figure 1) indicated that the
Au cores of 1 and 2 have fcc symmetries. Figure 2 shows
UV-vis-NIR absorption spectra of 1 and 2. The spectrum

Figure 1. Powder XRD patternsof 1 (black) and 2 (gray). (CuKα)

exhibits humps in the UV-vis region and, more surprisingly,
peaks in the NIR region (1070 and 1380 nm for 1 and 2,
conductedalow-temperature

UV-vis-NIR

absorption

measurement of 1. With decreasing the temperature, the NIR
peak was blue shifted as in the case of thiolate-protected
Au25(SR)18 and Au38(SR)24 [2]. This result indicates that the
NIR absorption peak is not associated with plasmon

Absorbance (a.u.)

respectively). To reveal the origin of the NIR region peaks, weresonance absorption, but optical transition between thequantized levels of 1.
References[1] P. Maity, et al., Nanoscale 4 (2012) 4027.
[2] M. S. Devadas, et al., J. Phys. Chem. Lett. 2 (2011) 2752.

500 1000 1500 2000 2500
Wavelength (nm)Figure 2. UV-vis-NIR spectraof 1 (black) and 2 (gray).

Optical properties and plasmonics

B23

Gold ultrathin nanowires and nanorods:
First observation of surface plasmon resonance
Ryo Takahata,1 Seiji Yamazoe,1,2 Kiichirou Koyasu,1,2 and Tatsuya Tsukuda1,2
1

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
2

ESICB, Kyoto University, Kyoto, Japan

Gold ultrathin nanowires (Au UNWs) with the diameter of ~1.6 nm and the length of several µm [1]will find applications in various fields by taking advantage of their high flexibility. The aim of thiswork is to study optical properties of the Au UNWs. To this end, we first prepared Au UNWs andultrathin nanorods (UNRs) by a method slightly modified with that reported in ref [2]. Typical TEM
images of three samples (Figs. 1a–1c) show that they have a common diameter of ~1.7 nm anddifferent average lengths of 370, 40, and 20 nm. These UNWs and UNRs exhibit strong extinction
bands in the IR region whose peak positions are redshifted with increase in the length (Figs.
1d–1f). This length-dependent shift of the band positions suggests that they are assignable to alongitudinal mode of surface plasmon resonance (SPR) [3]. In order to confirm this assignment,
we aligned the Au UNWs on an aminosilane-coated glass plate and measured their polarized
extinction spectra. The extinction in the IR region was enhanced when the incident light waspolarized parallel to the longitudinal axis of Au UNWs. This result supports our assignment of theIR band to a longitudinal mode of SPR [4].

Figure 1. a)–c) Typical TEM images and d)–f) optical extinction spectra of Au UNWs and UNRs
with the lengths of 370, 40, and 20 nm, respectively. The asterisks indicate vibrational peaks of
OA.
References[1] A. Halder et al., Adv. Mat. 19 (2007) 1854.
[2] H. Feng, et al., Chem. Commun. (2009) 1984.
[3] X. Lopez-Lozano, et al., Phys. Chem. Chem. Phys. 16 (2014) 1820.
[4] R. Takahata, et al., J. Am. Chem. Soc. 136 (2014) 8489.

Optical properties and plasmonics

B24

Controlled formation of highly luminescent silver clusters in zeolite matrices
via high-brilliance soft X-ray irradiation
Didier Grandjean,1 Eduardo Coutino-Gonzalez,2 Maarten Roeffaers,3 Kristina Kvashnina,4 Eduard
Fron,2 Bert Sels,3 Johan Hofkens,2 Peter Lievens1
1

Department of Physics and Astronomy, Laboratory of Solid State Physics and Magnetism,
KU Leuven, Celestijnenlaan 200D, B-3001 Leuven, Belgium
2

Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.

3

Department of Microbial and Molecular Systems, Centre for Surface Chemistry and Catalysis,
KU Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium.

4

European Synchrotron Radiation Facility (ESRF), CS40220, 38043 Grenoble Cedex 9, France

Oligoatomic (noble) metal clusters feature very peculiar optical and catalytic properties making
them very attractive for applications in diverse fields such as plasmonics [1], catalysis [2], andphotonics [3]. Template-mediated strategies in which the size and the shape of the metal cluster
are controlled by the dimensional restrictions induced by the hard template structure during thecluster formation are nowadays widely used to produce metal clusters with well-defined sizes andshapes. Popular templating host structures include glassy matrices, metal-organic frameworks,
and zeolites. Formation of sub-nanometer highly luminescent silver clusters via a thermal and/or aphoton-induced approach has been reported in glasses [4] but mostly in zeolite matrices where aclear relationship between the luminescence properties and the size of the Ag-clusters could bedemonstrated both in heat-treated [5] and photon-activated [6] Ag-exchanged zeolites.
In parallel to the utilization of different host systems, the development of highly controlled
activation procedures appears now crucial for the production of well-defined oligoatomic metalclusters.

In this work we explored the formation of silver clusters with very homogeneous

luminescence properties under high-brilliance synchrotron soft X-ray controlled irradiation indifferent zeolite topologies containing sodalite cages [7]. The optical properties of the formed
luminescent Ag-clusters were subsequently investigated by employing a combination of stationary
and time-resolved spectroscopic techniques and systematically compared to heat andphoto-activated samples with the same composition. Compared to conventional heat-treatment,
activation of silver zeolites with X-rays provides a more tightly controllable spatial production ofsilver clusters with very homogeneous luminescent properties at much faster time scales.
Reference(s)[1] K.G.M. Laurier, M. Poets, F. Vermortele et al., Chem. Commun. 48 (2012) 1559.
[2] K. Shimizu, K. Sawabe and A. Satsuma, Catal. Sci. Technol. 1 (2011) 331.
[3] A. Royon, K. Bourhis, M. Bellec et al., Adv. Mater. 22 (2010) 5282.
[4] K. Bourhis, A. Royon, G. Papon et al., Mater. Res. Bull. 48 (2013) 1637.
[5] G. De Cremer, E. Coutino-Gonzalez, M. Roeffaers et al., J. Am. Chem. Soc. 131 (2009) 3049.
[6] G. De Cremer, Y. Antoku, M.B.J. Roeffaers et al., Angew. Chem. Int. Ed. 47 (2008) 2813.
[7] E. Coutino-Gonzalez, D. Grandjean, M. Roeffaers et al., Chem. Commun. 50 (2014) 1350.

Optical properties and plasmonics

B25

One-step Synthesis and Characterization of Benzenthiol Derivative-protectedGold Clusters
Takuya Ishida,1 Yukina Takahashi,2 Hiroaki Okamura,3 Junichi Kurawaki,3 and Sunao Yamada2
1

Department of Materials Physics and Chemistry, Kyushu University, Fukuoka, Japan2

3

Department of Applied Chemistry, Kyushu University, Fukuoka, Japan

Department of Chemistry and Bioscience, Kagoshima University, Kagoshima, Japan

It is known that gold clusters (AuCs) consisting of a few
atoms exhibit unique character. It has been reported that
AuCs show molecule-like transition due to the discreteenergy levels according to the simple relation EFermi/ N1/3,
predicted by the spherical Jellium model1. There are Figure 1. Formula of BD1.
numerous reports for the use of organic thiols as cappingand functionalizing agents for AuCs. Although these synthetic approaches of functionalized AuCs
have been proposed, the methods have required multistep process and reagents such as
reducing and capping agents. In order to utilize AuCs for nanoscale devices, establishment of thesimple synthesis methods of functionalized AuCs is needed.
The benzenethiol derivative (BD1) (Fig. 1) was used as a reductive stabilizer for the formation of
AuCs. The BD1 is a model compound to develop a new one-step synthesis method offunctionalized AuCs. We could synthesize AuCs by just mixing aliquots of ethanol solution of BD1
and HAuCl4.
The absorption edge and emission maxima excited at 355 nm were observed at ~350 nm and~460 nm, respectively (Fig. 2). 1H-NMR spectrum of BD1-protected AuCs exhibited the lower
magnetic field shift of the proton of the benzene than that of the free BD1. It should be associatedwith an Au-S interaction. The organic-soluble photoluminescent BD1-protected AuCs was
assigned to Au9(BD1)6 mainly by optical spectroscopy and MALDI-TOF-mass.
Reference[1] J. Zheng, P. R. Nicovich, R. M. Dickson, Annu. Rev. Phys. Chem. 58 (2007) 409.
(a)

(b)

Figure 2. (a) The UV-vis and the secondary differentiation (inset) spectra of BD1-potected
AuCs. (b) Excitation (dashed) and emission (solid) spectra of the AuCs. Inset shows emission
under UV irradiation (365 nm).

Optical properties and plasmonics

B26

Ultrafast Strong Field Ionization of Small Metal Clusters
Dennis Dieleman, Valeriy Chernyy, Theo Rasing, Andrei Kirilyuk
Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands
In this work we investigate the interaction of strong (~1e15 W/cm2) and short (40 fs) laser pulses
with transition metal (Fe, Co, CoRh, CoAu) and lanthanide (Pr, Ho) clusters. For low laser
intensities the electrical field that is generated by the light can be treated as a small perturbation to
the clusters using standard perturbation theory. When we increase the intensity of the laser
however, these electrical fields become of the same or larger strength, than the Coulomb forcesthat hold matter together. This means the field can no longer be treated as a small perturbation,
which opens the way for a whole new range of interesting phenomena.
For example, in a cluster, interaction with an intense laser pulse can ionize the electrons of its
constituent atoms almost instantaneously. This so called inner ionization can create a nanoplasmaof quasi-free electrons inside the cluster, which has been shown to influence the ionization rate ofsmall metal clusters [1] and be the precursor to phenomena like Coulomb explosion and XUVradiation [2].
We have measured the laser intensity dependency on the ionization rates of small metal clusters,
varying the intensity by about 6 orders of magnitude (1e9 – 1e15 W/cm2). This wide range gives
us the possibility to explore the transition region between moderate fields, where multi-photon
effects dominate the ionization, and strong fields where mostly the laser field strength influences
the ionization dynamics.
For FeNOM, CoNAuM, CoNRhM, HoNOM and PrNOM clusters, with N ~ 1-10 and O ~ 0-3 we havedetermined the ionization energy (Ei) using two different models. For the low field multi-photon
region we find a good estimation of Ei using the fact that the rate of ionization is equal to theamount of photons necessary for ionization. In the strong field region we use the Barrier
Suppression Intensity as measure for Ei, which basically relates the field strength of the laser
needed to suppress the coulomb barrier, to Ei. For both models we find good agreement withliterature in the case of Fe and Pr. Which shows that this method can also be applied for the doped
cobalt clusters, for which Ei was not yet measured before.
Finally we study the influence of the pulse width (40 fs – 5 ps) on the ionization rate and find astronger dependence on pulse width for CoRh than for Ho and Pr clusters. For Fe clusters we see
clear signs of Coulomb explosions even at unexpected moderate intensities when going to shorter
pulses.
References:[1] Smits, M., de Lange, C., Stolow, A., & Rayner, D., Phys. Rev. Lett., 93(20), (2004), 203402.
[2] Fennel, T., Meiwes-Broer, K.-H., Tiggesbäumker, J., Reinhard, P.-G., Dinh, P. M., & Suraud, E.
Reviews of Modern Physics, 82(2), (2010) 1793–1842

B27

Carbon-based nanomaterials

Monocarbon cationic cluster synthesis from methane-nitrogen mixturesembedded in He nanodroplets and their calculated binding energies
Iogann Tolbatov1,2, Sylwia Ptasinska1,2 and Daniel M. Chipman1
1

Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556, USA

2

Department of Physics, University of Notre Dame, Notre Dame, IN 46556, USA

Helium nanodroplets are a unique tool for assembly and study of reactions in various molecularcomplexes due to their superfluidity at low temperatures and the high ability to be doped. In ourstudy,

processes

relatedtomolecule

andclusterformationinirradiatedgaseousmethane-nitrogen mixtures in helium droplets are investigated. The molecular structures formed
from N2/CH4 mixtures of different concentrations were trapped with the help of an ultracold
environment of helium nanodroplets. A beam of low-energy electrons (70 eV) was used for theirradiation. Afterwards, the results of irradiation were analyzed by the TOF mass spectrometer.
From the experiment, it was deduced that all the monocarbon clusters studied are most likely to beformed in the range of 5%–30% of methane in the mixture. A variety of clusters and molecules
were observed with the mass to charge ratio up to 80 Da. The synthesized structures wereanalyzedbyquantumchemicalcalculations

using

the

CCSD(T)/6-311G(2d,p)//

CCSD/6-311G(2d,p) method.

Fig. 1 Ion yield and binding energy values of monocarbon molecular complexes
A summary of the resulting products and their ion yields is shown in Fig.1. Molecular complexes
CHN2+, CHN4+, and CH2N2+ exhibit a strong energetical favorability towards C=C-N ringformation. Molecule CH3N2+ has the greatest ion yield and a rather high binding energy of 1.57
eV. Otherwise there is little correlation between the ion yields and the associated binding energies,
indicating that kinetic control is more important than thermodynamic control for forming theclusters in most cases.

Carbon-based nanomaterials

B28

Genuinely amorphous carbon produced from explosive nano acetylide
Ken Judai,1 Naoyuki Iguchi,1 and Yoshikiyo Hatakeyama1
1

Department of Physics, College of Humanities and Sciences, Nihon University, Tokyo, Japan

Copper acetylide and silver acetylide are famous as explosive compounds. However, when the
explosive crystals are downsized into nanoscale, the explosive nature will be eliminated by much
lower thermal conductance preventing the crystals from explosive chain reactions. This nanoless-explosive character can be applied to new noble carbon material production.
Generally amorphous carbon is prepared by exposing organic compounds to high temperature forcarbonization. The high temperature for carbonization affects the crystallization to graphite
partially. In this new method, the carbonization reaction can proceed with lower annealing
temperature because of chemical reactive nature of copper acetylide, and genuinely amorphous
carbon materials can be prepared.
The following figure shows the Raman spectrum of new carbon materials prepared by lower
temperature carbonization of copper acetylide nano compounds and acid treatment for removal ofcopper element. The peak around 1600 cm-1 assigned to G-band was observed in a similarfeature to the typical carbon materials, and the peak about 1380 cm-1 assigned to D-band as well.
However, the spectrum in this method showed extremely broader peaks than those of the typicalcarbon materials, and the G-band and the D-band were deeply overlapped. This suggests thegenuinely amorphous state of carbon

Figure: Raman spectrum of genuinely amorphous carbon. Copper
acetylide nano materials could be carbonized at a temperature of 200°C.

B29

Carbon-based nanomaterials

Evaluation of the ratio of metal/semiconductive single-wallcarbon nanotubes separated in two immiscible aqueous
solution phases by utilizing Raman spectroscopy
Shinzo Suzuki,1 Naoki Kanazawa,1 Akira Ono,2 and Yohji Achiba,3
1
2
3

Department of Physics, Kyoto Sangyo University, Kyoto, Japan

Department of Engineering, Kanagawa University, Kanagawa, Japan

Department of Chemistry, Tokyo Metropolitan University,Tokyo, Japan

In 2013, C.Y. Khripin et al. reported about spontaneous partition of single-wall carbon nanotubes(SWNTs) in polymer-modified aqueous solution phases [1], where metal/semiconductive SWNTsof large diameter (> 1.2 nm) are shown to be easily separated in two immiscible aqueous solution
phases, i.e., polyethylene glycol (PEG) and dextran (DX) aqueous solution. In this presentation,
Raman spectroscopy technique was applied to each aqueous solution phase, in order to evaluate
the ratio of metal / semiconductive SWNTs by changing excitation photon energy (532 nm and 633
nm).
Briefly, mono-dispersed sodium cholate (SC) solution (2wt%) of SWNTs produced by arc-burningof Ni/Y-carbon composite rod in helium atmosphere was utilized for two immiscible aqueous
solution, following the recipe by C.Y. Khripin et al. [1]. After recognizing that PEG sand DX solution
phases show different colors because of the difference in the ratio of metal/semi-conductive
SWNTs, Raman spectra of each phases were obtained by different excitation photon energy (532
nm and 633 nm). Typical example of Raman spectra (G-band region) for PEG and DX solution
phase by excitation photon energy (532 nm and 633 nm) were shown in Figures 1 and 2,
respectively. It was clearly shown that the ratio of semiconductive SWNTs to metallic ones washigher in PEG solution phase than that in DX solution phase.

PEG

DX

Figure 1.

Figure 2.

Reference[1] C.Y. Khripin et al., J. Am. Chem. Soc., 135, 6822-6825(2013).

Carbon-based nanomaterials

B30

Growth of single-wall carbon nanotubes on the porous
glass (PG) sheet by using ACCVD technique
Shinzo Suzuki,1 Kyohei Nagao,1 Yosuke Ito, 1
Nobuaki Ito, 2 Hiroshi Nagasawa, 3 and Yohji Achiba4
12Department of Physics, Kyoto Sangyo University, Kyoto, Japan

Center for Nano Materials and Technology, JAIST, Ishikawa, Japan
3

4

Nano-support Co. Ltd., Kanagawa, Japan

Department of Chemistry, Tokyo Metropolitan University, Tokyo, Japan

ACCVD technique has been widely used for the growth of single-wall carbon nanotube (SWNT),
because that the ambient temperature for the formation of SWNTs is relatively low (typically, lessthan 800°C), and the purity of SWNTs in as-grown material is considered to be better than thoseobtained by other technique, e.g. arc-burning procedure.
Aoki et al., reported in 2005, about the formation of SWNTs in the porous glass (PG) material byusing ACCVD technique [1], where a kind of metal particles (e.g. Co particles) were deposited on
the PG material before ethanol as carbon source was introduced for making SWNTs in thematerial. The advantage of using PG material is that, it is very easy to make any kind of shape (rod,sheet.., etc.) made of PG, which implies that the as-grown PG-SWNT complex material itself canalso be applied for e.g., optical or electronic devices.
In this presentation, PG-sheets having different pore size (10nm, 30nm, 50nm, and 100nm,
respectively) were prepared and tested for SWNT growth by using ACCVD technique. After
optimizing the condition for SWNT growth, Raman spectroscopy and SEM technique were applied
for the obtained SWNT-PG complex material, in order to characterize the purity and the diameter
distribution of SWNTs grown on each PG-sheet.
Reference[1] Y. Aoki, S. Suzuki, S.Okubo, H. Kataura, H. Nagasawa, and Y. Achiba, Chem. Lett., 34,562(2005).

Carbon-based nanomaterials

B31

Analysis of the products of single-walled carbon nanotube growthwith the aid of density functional theory calculations
1

Arne Rosén*, 2Yunguo Li, 4J. Andreas Larsson, 3Hamid Reza Barzebar and 3Thomas Wågberg
1

Professor em, Department of Physics, University of Gothenburg, SE-412 96 Gothenburg Sweden
2
Department of Materials Science, Royal Institute of Technology,
SE-100 44 Stockholm, Sweden
3
Department of Physics, Umeå University, SE-901 87 Umeå, Sweden
4
Applied Physics, Division of Materials Science, Department of Engineering Sciences andMathematics, Luleå University of Technology, SE-971 87 Luleå, Sweden

1. We report use of a dip-coating method to prepare catalyst particles (mixture of iron andcobalt) with a controlled diameter distribution on silicon wafer substrates by changing the solution
concentration and withdrawal velocity [1].The size and distribution of the prepared catalyst particles
were analyzed by atomic force microscopy. Carbon nanotubes were grown by chemical vapor
deposition, CVD, on the substrates with the prepared catalyst particles. By decreasing the particle
size, the growth of carbon nanotubes can be tuned from few walled carbon nanotubes, withhomogeneous diameters, to highly pure single walled carbon nanotubes, SWNT. Analysis of theRaman radial breathing mode, showed a relatively broad diameter distribution (0.8-1.4 nm) of
single walled carbon nanotubes, SWNT, with different chiralities. By changing the size andcomposition of the catalyst particles but maintain the growth parameters, the chiralities of SWNT
were reduced to mainly four different types: (12,1), (12.0), (8,5) and (7,5) of which quantity is 70 %of all the nanotubes.
2. A deeper understanding of the growth mechanism of nanotubes by the CVD is usually doneusing a modified version of the established vapor-liquid-solid (VLS) method for production of
nanowires. For successful growth the catalytic metal particles should be able to: (i) decompose thefeed-stock gas, (ii) form graphitic caps at their surface and (iii) stabilize of the growing open end tomaintain the hollow structure. Recently criterion (iii) was identified and shown to be fulfilled using
Density Functional Theory, DFT, calculations [2,3],when the metal-carbon bond is strong enough tomake the dissociation of the catalytic particle and the SWNT unfavorable. Too week metal-carbon
bond cannot stabilize the open CNT end. For investigation of the relative stability of hydrogenterminated SWNTs fragments of varying diameter and chirality we have performed electronic
structure DFT calculations. Our calculations for tube segments of (n+m) = 9 - 13 tubes show that
there is no telling if armchair/armchair-like or zigzag/zigzag-like tubes are the most stable within aseries. However, the most stable tubes in the series from our calculations are the ones mostfrequently seen when characterizing the products of SWNT growth.
Reference(s)[1] H. R. Barzegar et al, J. Phys. Chem. C116,12232 (2012)[2] F. Ding, P. Larsson, J. A. Larsson, R. Ahuja, H. Duan, A. Rosén, K. Bolton,
Nano Lett. 8 (2008) 463.
[3] J. D. Baran, W. Kołodziejczyk, P. Larsson, R. Ahuja, J. A. Larsson,
Theor. Chem. Acc. 131,1270 (2012)Carbon-based nanomaterials

B32

Bonding and Spin-polarized Transport of Co Atomic Chainon Graphene with Topological Line Defects
Cheng-huan Jiang,1, 2 Gui-xian Ge,1 Jian-guo Wan1*, and Guang-hou Wang
1

National Laboratory of Solid State Microstructures, and Department of Physics, Nanjing
University, Nanjing 210093, China
2

School of media technology, Communication University, Nanjing, China

Graphene is regarded as a potential material for future spintronics due to its extremely longmean-free path and large spin relaxation time.1 Transition metals (TMs) adsorbed on pristinegraphene exhibit high local magnetic moment,2 however, TMs have relatively weak bonding withgraphene and easily diffuse with low barrier.3 Recently, it is reported that the ‘5-5-8’ extended line
defect (ELD) can be produced on graphene in a controllable way.4 In this work, based on thefirst-principle calculations we focus on the investigation of a hybrid system consisting of cobalt
atomic chain on graphene with 5-5-8 ELDs. Our results show that the hybrid system has arelatively large binding energy (~0.7 eV/Co) and a high diffusion barrier (~1.2 eV) of Co atoms ongraphene, indicating that the Co chain is stable on the system (Figure (a)). Moreover, we find thatthe interaction between the aggregates comprised of eight Co atoms can generate stableferromagnetic coupling. Further calculations based on the non-equilibrium Green’s function
method show that the system exhibits spin-dependent current-voltage (I-V) behaviors with current
polarization of ~30% at 0.4 V (Figure (b)). Such unique spin-polarized transport property suggeststhat the present system may be served as a building block for future spintronic devices.

Figure. (a) Binding energy per Co atom as a function of the Co chain size (n). The insets aresecond difference Δ2E(n) as a function of n. (b) Spin-dependent I-V curves for the hybrid system.
References[1] X. Du, I. Skachko, A. Barker, and E. Y. Andrei, Nature Nanotechnology 3 (2008) 491.
[2] I. Zanella, S. B. Fagan, R. Mota, and A.Fazzio, J. Phys. Chem. C 112 (2008) 9163.
[3] O. V. Yazyev, A. Pasquarello, Phys. Rev. B 82 (2010) 045407.
[4] J. H. Chen, G. Autes, N. Alem, F. Gargiulo, A. Gautam, M. Linck, C. Kisielowski, O. V. Yazyev,
S. G. Louie, and A. Zettl, Phys. Rev. B 89 (2014) 121407(R).

Carbon-based nanomaterials

B33

Metallic sp2 carbon nanomaterials with octagons showing high density of statesat the Fermi level: A first principles study
Yusuke Noda, Shota Ono, and Kaoru Ohno
Department of Physics, Graduate School of Engineering, Yokohama National University,
Yokohama, Kanagawa, 240-8501, Japan
Carbon-based nanomaterials are expected to be useful for wide variety of applications. Since thesuccessful synthesis of monolayer graphene [1], much attention has been paid to its electronic
properties, in particular massless Dirac fermion-like behavior in the vicinity of the Fermi level dueto the existence of the Dirac cone. This property leads to high electron mobility appropriate fordeveloping carbon-based electronic devices. However, this property is not suitable for new
materials alternative to precious metals because the density of states (DOS) at the Fermi level isexactly zero. Exhibiting a high DOS at the Fermi level is a very important characteristic of precious
metals such as platinum and palladium [2-4]. If one could additionally introduce a high DOS ingraphene, it could find a wide range of applications such as for high-carrier-density, catalytic,
superconducting, thermoelectric, ferromagnetic, and other functional materials.
We investigated electronic states of various sp2 carbon nanomaterials [one-dimensional
peanut-shaped fullerene polymers [5] and corrugated graphene systems (see Fig.1)] using density
functional calculations. We found that the presence of “isolated” octagons (surrounded bypentagons and hexagons, not adjoined to any heptagon and other octagon) in a unit cell brings
about the simultaneous occurrence of flat and dispersive bands, and the flat band leads toextremely high DOS, quite similar to the electronic state of precious metals [6]. Such defects will
provide a fertile playground for physics, chemistry, and technological applications of new
carbon-based nanomaterials.

Fig.1 Geometrical structure, band structure, and DOS of corrugated graphene (Fermi energy is set at 0.0 eV)

References[1] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, M. I. Katsnelson, I. V. Grigorieva, S. V.
Dubonos and A. A. Firsov, Nature 438 (2005) 197.
[2] O. K. Andersen, Phys. Rev. B 2 (1970) 883.
[3] H. Chen, N. E. Brener and J. Callaway, Phys. Rev. B 40 (1989) 1443.
[4] V. Theileis and H. Bross, Phys. Rev. B 62 (2000) 13338.
[5] J. Onoe, T. Ito, H. Shima, H. Yoshioka, and S. Kimura, Europhys. Lett. 98 (2012) 27001.
[6] Y. Noda, S. Ono, and K. Ohno, Phys. Chem. Chem. Phys. 16 (2014) 7102.

B34

Carbon-based nanomaterials

Simultaneous formation of fullerenes and polyynes
by laser ablation in the gas phase at room temperature
Hitomi Endo,1 Yuki Taguchi,1 Yurika Abe,1
Tomonari Wakabayashi,2 Takeshi Kodama,1 Yohji Achiba,1 and Haruo Shiromaru1
1

Department of Chemistry, Tokyo Metropolitan University, Hachioji, Japan2

Department of Chemistry, Kinki University, Higashi-Osaka, Japan

Carbon clusters formed by laser ablation of graphite are generally grouped into linear chains,
hollow cages, and rings, of which the former two are isolated as polyynes and fullerenes,
respectively. These are usually produced under far different conditions from each other; laser
ablation in an organic solvent for polyynes and laser ablation in a high-temperature rare-gas
environment for fullerenes. Recently, we found that polyynes and fullerenes are co-produced bylaser ablation of graphite in Ar gas flow [1]. In the present study, we examined the effect ofpropane as a hydrogen source mixed in the Ar gas. Total gas flow rate was 100 mL/min withvarious propane flow rates from 0 to 1 mL/min (0 to 1% propane). Laser ablation was performed atroom temperature in a glass tube with a cone-shaped exit for gas and the ablation products werecarried into cooled hydrocarbons at the bottom of a glass bottle. The product molecules wereseparated by HPLC with an eluent of hexane, and analyzed by UV-Vis absorption.
A HPLC-UV two dimensional spectrum of atypical product solution prepared by laser
ablation in 1% propane is shown in Fig. 1, where
the characteristic UV bands of C8H2, C10H2,
C12H2, and C60 are clearly observed at 227 nm,
252 nm, 276 nm, and 257 nm, respectively.
Fullerene formation was confirmed also for laser
ablation in 0 - 0.25% propane. The laser ablation
conditions for fullerene formation have so far
been extensively studied and high-temperature
rare gas is considered to be indispensable. The
fullerene formation at room temperature is
therefore most likely due to local heating of theglass tube by laser irradiation. The yield ofpolyynes strongly depends on the propane
concentration. The ablation in 0.25% propane
enhances the yield significantly.

Figure 1 Two dimensional spectrum of decalin
solution prepared by laser ablation in 1% propane.
The inset is UV absorption spectra at retention time
4.6 min.

Reference[1] Y. Abe et al., The 46th Fullerene-Nanotubes-Graphene General Symposium (2014) 141.

B35

Carbon-based nanomaterials

Pressure dependence of production of carbon nanotubes
by High-temperature Pulsed-arc Discharge
Hayato Kikuchi,1 Atsushi Shimaya,1 Hiroki Koizumi,1 Ryota Jinnouchi,1Katsuhide Terada,2 Toshiki Sugai1
1
2

Department of Chemistry, Toho University, Funabashi, Japan

Faculty of Pharmaceutical Sciences, Toho University, Funabashi, Japan

A high-temperature pulsed-arc discharge (HTPAD)
has been developed to produce carbon nanotubes(CNTs). The system utilizes width controlled
pulsed-arc discharge

for thevaporizationofelectrodes in a temperature controlled ambient gas.
With those width and temperature controls, novel
materials have been produced such as high-quality
double wall carbon nanotubes [1]. Since the CNT
production of laser and arc related methods are
dominated by the gas pressure [2,3], here we
present the pressure dependence of HTPAD up to
5 atm to investigate the processes. The standard

Fig. 1 Pressure Dependence ofsteady arc discharge is rarely performed in such

CNT concentrations obtained by TGA

high pressures [3].
The details of HTPAD described in elsewhere [1]. Electrodes made of graphite containing catalytic
metals (Ni/Y 4.2/0.5 and 4.2/1.0 at. %:Toyo Tanso Co. Ltd.) were vaporized by the pulsed-arc
discharges (0.6 ms, 50Hz, and 100 A) and were converted into CNTs in the high-temperature(1250 ℃) and a wide pressure range of Ar (0.2-5 atm). The products were characterized by
Raman spectroscopy with excitation laser of 633 nm, TGA, and TEM.
Figure 1 shows the pressure dependence of concentration of CNTs obtained by TGA. The optimalpressure is 1.5 atm in every characterization method. The analyses on the optimal pressure ofvarious conditions such as gas species and temperature have shown that the production
processes are mainly dominated by cooling and condensation processes [3]. Our optimal
condition of 1.5 atm is exactly corresponding to those obtained by the analyses, which is marked
as a shaded area in Fig. 1. The agreement shows that the cooling processes are also crucial for
HTPAD even though there are so many differences in vaporization processes.
References[1] T. Sugai et al., Nano Lett. 3 (2003) 769.
[2] O. Jost, A. A. Gorbunov, J. Möller, W. Pompe, X. Liu, P. Georgi, L. Dunsch, M. S. Golden, and
J. Fink, J. Phys. Chem. B 106 (2002) 2875.
[3] Y. Saito, Y. Tani, and A. Kasuya, J. Phys. Chem. B 104 (2000) 2495.

B36

Device-oriented topic

Ligand exchange reactions on transition metal oxo clusters and applications inmaterials chemistry
Johannes Kreutzer, Ulrich SchubertInstitute of Materials Chemistry, Vienna University of Technology, Vienna, Austria
Transition metal oxo clusters find increasing interest in material science as nanosized building
blocks, especially for inorganic-organic hybrid materials. Clusters with polymerizable ligands
attached to the cluster surface can act as co-monomers in polymer synthesis. Thereby the
inorganic moiety is incorporated in a polymer matrix by covalent bonding. Numerous transition
metal oxo clusters with polymerizable ligands were synthesized and used to obtain polymers with
tailored properties.
Most of the clusters used as co-monomers so far have a high number of polymerizable groups ofthe same kind on their surface, resulting in highly crosslinked polymers. Ligand exchange ontransition metal oxo clusters is one way to control the ratio of functionalized and nonfunctionalized ligands and can lead to less crosslinked polymers. Furthermore it is possible toobtain clusters with more than one functional group in the ligand sphere in an easy-to-adjust ratio
by ligand exchange reactions.
In this work we will present a detailed NMR study of exchange reactions on carboxylate
substituted Zr/Ti oxo clusters with different carboxylic acids. We will show that ligand exchangeon the cluster proceeds under retention of the cluster core also in cases where all ligands havebeen exchanged. Steric and electronic effects of the incoming ligand towards exchange reactions
will be discussed. Scrambling reactions between clusters with two different types of ligands arean additional way to easily adjust the ligand composition of transition metal oxo clusters.
Complementary applications of ligand exchange reactions in material science will be presented.
Polymer properties such as glass transition temper
ature and storage modulus as well as mechanical properties of the polymer can be changed
gradually by controlling the ligand sphere of transition metal oxo clusters.

Device-oriented topic

B37

Extending the Sizes and Charge States of Polyanionic Metal Clusters
Steffi Bandelow,1 Franklin Martinez,1,2 Gerrit Marx,1 Lutz Schweikhard,1 and Albert Vass1
1

Institute of Physics, Ernst-Moritz-Arndt University Greifswald, Germany

2

present address: Institute of Physics, University of Rostock, Germany

The ClusterTrap setup [1] combines several ion-storage devices for a variety of experimental
studies on metal clusters including collision-induced dissociation, (delayed) photodissociation,
further ionization to higher positive or negative charge states by electron impact or electron
attachment, respectively. All selection, preparation and interaction steps can be performed on
extended time scales up to several seconds. The unique arrangement of two linear radiofrequency
quadrupole (RFQ) ion traps (Paul traps) and an ion-cyclotron-resonance trap (ICR or Penningtrap) allows one to dedicate them with respect to specific functions and optimizations.
In particular, one Paul trap is used for the accumulation of cluster ions from a pulsed laservaporization source and preselection of the cluster size. In the second Paul trap, electrons can be
attached at well-defined energies by use of a “digital” (i.e. rectangular) RF trapping potential [2].
This allows one to study for the first time the energy dependence of electron attachment topolyanionic metal clusters and to determine the heights of their repulsive Coulomb barriers. With arecent replacement of the superconducting magnet, the field strength was increased from B = 5 T
to 12 T. Thus, the electron attachment in the ICR trap was extended to (negative) charge states ashigh as z = -6 for gold and z = -10 for aluminum clusters, respectively. The yields of the charge
states measured as a function of reaction time confirm a sequential electron-attachment process.
Next, we will study polyanion decay induced by laser light. The studies will be performed withrespect to cluster size, charge state and chemical element as well as laser intensity and photon
energy, and also regarding possible delays between photo-interaction and electron detachment orcluster dissociation. Furthermore, it is planned to use multi-reflection time-of-flight mass
spectrometry, recently further developed by us for precision measurements in nuclear physics [3],for high-resolution separation of the (relatively large) polyanionic cluster, and to combine ion-trap
techniques of polyanion production with their investigation by photo-electron spectroscopy.
[1] L. Schweikhard et al., Eur. Phys. J. D 9 (1999) 15; F. Martinez et al., Eur. Phys. J. D 63 (2011)
255; F. Martinez et al., Int. J. Mass Spectrom. 365-366 (2014) 266.
[2] S. Bandelow et al., Int. J. Mass Spectrom. 336 (2013) 47 and 353 (2013) 49.
[3] R.N. Wolf et al., Int. J. Mass Spectrom. 349-350 (2013) 123; F. Wienholtz et al., Nature 498(2013) 346.

B38

Device-oriented topic

Surface immobilization of gas-phase-synthesized nanoclusters toward
construction of nanoelectronics
Masato Nakaya,1,2 Takeshi Iwasa,1,2 Hironori Tsunoyama,1,2
Toyoaki Eguchi,1,2 and Atsushi Nakajima1,2,3
1

Nakajima Designer Nanocluster Assembly Project, JST, Kawasaki, Japan2

Department of Chemistry, Keio University, Yokohama, Japan

3

Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, Yokohama, Japan

Constructing nanoelectronics from nanocluster building blocks is one of the most attractive
challenges in nanocluster science, since it has been actively demonstrated that various functional
nanoclusters can be created in gas phase and their physicochemical properties are controllable bychanging their size, compositions, and charge states. In this study, we have created ultrathin
metal/molecule and acceptor/donor junctions using the gas-phase-synthesized nanoclusters.
The metal/molecule junctions were formed by depositing size-selected Ag nanocluster cations(Agn+; n = 7, 13, and 55) onto few-layer C60 films and were investigated by scanning tunnelingmicroscopy and spectroscopy (STM/STS) [1]. The Agn are stably immobilized without marked
disintegration on the C60 films and can densely cover the surface (Figure 1). In addition, charged
carriers can be precisely injected into the topmost C60 layers via the Agn. These results indicatethat the atomically abrupt interface can be formed between the Agn and C60 films. This is attractive
toward realizing high performance devices composed of metal/molecule/metal junctions, because,in the conventional sandwich junctions constructed by depositing metal atoms onto molecular films,
undesirable modification of the molecular films generally occurs by penetration of the metal atoms.
Furthermore, barrier heights for the carrier injection at
the Agn/C60 interface can be controlled depending on
the cluster size and deposition conditions.
We

have

also

depositedthetantalum-atom-

encapsulated Si16 cage cations (Ta@Si16+) from gas
phase where they behave as superatoms with raregas-like features. It has been found that the Ta@Si16
are densely immobilized onto C60 films while maintaining
the cage shape, large energy gap of ~2.1 eV, and highthermal durability similar to those in gas phase. In
contrast, the Ta@Si16+ are destabilized on bare andoligothiophene-terminated metallic surfaces. STS andtheoretical results indicate that positive charge isretained in the surface-immobilized Ta@Si16 by forming
the charge transfer complex (Ta@Si16+-C60−).
Reference

Figure 1. C60 thin films (upper) sparselyand (lower) densely covered with Ag55

[1] M. Nakaya, T. Iwasa, H. Tsunoyama,T. Eguchi, A. Nakajima, Adv. Funct. Mater. 24(2014)1202.

Device-oriented topic

B39

Generation of small and stable Si nanoparticles using a liquid jet co-deposition
methodGediminas Galinis1, Oliver Youle1, Hanieh Yazdanfar1, Mike J. McNally1, Mumin M. Koç1,
Gauthier Torricelli1, Mark Watkins1, Klaus von Haeften1.
1

University of Leicester, Department of Physics & Astronomy, Leicester, LE1 7RH, United
Kingdom

Small and stable nanoparticles are particularly interesting due to their exotic physical and opticalproperties. These nanoparticles are applicable in opto-electronics [1] and may be used as
biosensors [2]. The methods currently available in industry to generate nanoparticles lack anability to prepare small (<5nm) and stable nanoparticles in liquids without further stabilization bysurfactants. We present a novel method to deposit sputtered semiconductor and metal atoms on
the surface of a liquid jet in vacuo and subsequent growth into stable and small clusters without
surfactants. This method is capable of generating large quantities (ml) of nanoparticle-solvent
mixtures within few minutes.
The presentation will focus on the generation and characterization of Si nanoparticles, whose
stability and sizes were determined by UV-Vis, XPS and AFM measurements. In the UV-Vis
spectra we identified a fingerprint of Si clusters; this peak showed a distinct intensity correlation to
the deposition rate of Si atoms sputtered from the Si target. Furthermore, time-resolved UV-Vis
spectra showed stabilization of Si nanoparticles within a 30 min interval. The sizes ofnanostructures were determined by drop-casting nanoparticle colloids on the surface of HOPG,
allowing the solvent to evaporate and subsequently probing the heights of residue nanoparticle
layers with AFM. A size of 1 nm nanoparticles has been thus demonstrated. Further support forthe presence of Si nanoparticles and their size was obtained from XPS measurements: themagnitude of Si-peak-shift suggested structures of a size of 1 to 2 nm [3].

References[1] K. M. Noone, and S. David Ginger, Acs Nano 3.2 (2009): 261-265.
[2] G. Wang, et al., Optics communications 281.7 (2008): 1765-1770.
[3] M. Vogel, et al., Physical Review B 85.19 (2012): 195454.

B40

Device-oriented topic

Enhanced quantum coherence in graphene by Pd cluster deposition and its
zero-temperature saturation
Fengqi Song, Junhao Han, Yuyuan Qin and Guanghou Wang
Department of Physics and National Lab of Solid State Microstructures,Nanjing University, 210093,
Nanjing, China
Surface absorption of functional atoms is believed to implement the quantum spin/anomalous hallstate. A problem arises that the surface absorption will simultaneously induce additional electronic
scattering while introducing the required functionalities. Such scatterings may suppress thecoherence of the Dirac Fermions and subsequently disable these desired quantum states. Here
we report the increase of the dephasing lengths of the graphene sheet after the deposition of Pd
nanoclusters [1] as demonstrated by weak localizations. The dephasing lengths are found to reachsome saturated values with the decreasing temperatures, essentially the zero-temperature
decoherence. Detailed analysis is carried out on the temperature-dependent and saturated
decoherence periods. Our data agree well with the predication of Golubev and Zaikin, where suchzero-temperature decoherence is mainly induced by local fluctuations of the electrical fields neardisorders. The competition between the surface scattering and electrical field screening leads tothe final improvement of quantum coherence. We propose the priority of using the nanoclusters
that less scattering is introduced while seeking the same control of the electronic interference
through absorbing the same quantity of atoms.

Figure. (a) The SEM image of the graphene sheet after the cluster deposition. (b) The relative magnetic
conductance ∆G(B) plotted against the perpendicular fields B at various temperatures. (c) Focusing on
the WL cusp at low temperatures. The two curves are the MR curves measured at 2K, before
deposition (blue) and 3K, after deposition (red) respectively. The cusp becomes much sharper after theabsorption of the Pd clusters, clearly indicating the improvement of the electronic coherence.

Structure and thermodynamics

B41

The hydrogen Bonded Networks in Hydrated Halogen Anions
Chiaki Ishibashi,1 Suehiro Iwata,2 Kaoru Onoe1 and Hidenori Matsuzawa1
1

Department of Engineering, Chiba Institute of Technology, Narashino, Japan2

Department of Chemistry, Keio University, Yokohama, Japan

Recently we have developed the ab initio theoretical procedure based on the Locally Projected
Molecular Orbital Perturbation Theory (LPMO PT), and applied it for the analysis of the water
clusters (H2O)n (n≦25) and their hydrogen bonded networks [1,2]. The present study is the ex-tension to the hydrated halogen anions X (H2O)n (n=1-7) clusters.
-

Various isomers of the X (H2O)n (n=1-7) cluster are determined with the MP2 method with
aug-cc-pvdz basis set. Some of them have the similar geometric structures in literature, and thecalculated binding energies are in good agreement with the reported values. The LPMO PT allows-

us to evaluate the charge-transfer (ECT) and dispersion (EDisp) terms for every pair of water-X andwater-water. In the earlier papers [1,2], the strong correlations between the ECT and EDisp andbetween ECT and the hydrogen bond length are found. The correlations are dependent on thetypes of water molecules involved.
The similar correlations are found also for the halogen-water and water-water hydrogen bonds in-

X (H2O)n. Figure 1 shows the correlation between the bond length RX-O of halogen and water vs.
ECT and EDisp in the Cl-(H2O)n (n=3-7) cluster is shown.
In the figure each water is classified by DnAm. For instance, water molecule of D0A2Cl has a Cl･･･H and
two O･･･HO bonds but no hydrogen bond to the watermolecule. Figure 1 shows that the D0A2Cl water molecule is most strongly interacted with Cl anion, because
this water molecule is more positively charged by accepting two HO bonds, or by electron-donating to theneighboring molecules. On the other hands, theweakest X-...H2O hydrogen bond of water molecule isof D1A0Cl type.

Figure 2 is the similar correlation

between RO-O of hydrogen-bonded pair of water molecules vs. ECT and EDisp in the Cl-(H2O)n. As was foundin the pure water clusters [1,2], the D1A2→D2A1 pairs
are the strongest among various pairs of the hydrogenbonds. In the D1A2→D2A1 bond pair, the hydrogen
donor water of D1A2 is strongly positive charged, andthe hydrogen acceptor water of D2A1 is less positive
than the other types of water molecules.
References[1] Iwata, Phys. Chem. Chem. Phys. 16 (2014) 11310[2] Iwata, Bandyopadhyay, Xantheas, J. Phys. Chem. A 117(2013) 6641

Structure and thermodynamics

B42

Formation of regular polyicosahedral structure during growth of large
Lennard-Jones clusters from their global minimum
Wieslaw Polak
Department of Applied Physics, Lublin University of Technology, Lublin, Poland
Monte Carlo simulations of growth of Lennard-Jones (LJ) clusters were carried out for reduced
temperature T * = 0.35 and seed clusters having the following structures and sizes: ideal
icosahedral (N = 561, 923), icosahedral with empty core (N = 850), and decahedral (N = 823)
reported as global minima by Xiang et al. [1]. After thermal equilibration, all these clusters weregrown using the cluster growth model [2] in 15 simulation runs up to N ≈ 3300 by attachments ofrandomly-moving atoms from supersaturated vapour of atom concentration n* = 0.001.

Linear dh chains and icosahedral units inside: (left) seed of N = 923, (right) final r-PIC cluster of N ≈ 3300.

Structural analysis and visualisation showed that internal structure (see Fig. above) of theequilibrated clusters practically did not change showing only existence of some dislocated atoms
on the cluster surface without any surface reconstruction. In all cases the growth leads toformation of regular polyicosahedral structure (r-PIC) in accordance with recent results [3].
Neighbouring local icosahedral units in the internal structure of the growing clusters are connectedby decahedral (dh) linear chains of length typically equal to the distance of vertex atoms fromcluster center in case of icosahedral clusters. This means that newly-added atoms attain positionstransforming the surface layer to hexagonal close-packed (hcp) monolayer characteristic foranti-Mackay packing [4]. Kinetic process in the form of creation of dh chain at a contact of two
such hcp monolayers is responsible for formation of the r-PIC structure.
References[1] Y. Xiang, L. Cheng, W. Cai and X. Shao, J. Phys. Chem. A 108 (2004) 9516.
[2] W. Polak, Phys. Rev. B 71 (2005) 235413.
[3] W. Polak, J. Crystal Growth 401C (2014), http://dx.doi.org/10.1016/j.jcrysgro.2014.01.017.
[4] J.P.K. Doye, D.J. Wales, Z. Phys. D 40, (1997) 466–468.

Structure and thermodynamics

B43

Structures and dielectric properties of neutral lead clusters
D.A. Götz,1 A. Shayeghi,1 R.L. Johnston2, P. Schwerdtfeger3, and R. Schäfer1
1

Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische Universität
Darmstadt, Alarich-Weiss-Straße 8, 64287 Darmstadt

2

School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, United
Kingdom

3

Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study,
Massey University (Albany), Bob Tindall Bldg., 0745 Auckland, New ZealandElectric molecular beam deflection experiments are an established method for resolving thestructures of neutral group 14 clusters [1]. For this purpose deflection profiles are modeled using
structures and dielectric properties from quantum chemical calculations and compared toexperimental data. Promising PbN (N=7-18) structures are located using the unbiased Birmingham
Cluster Genetic Algorithm in combination with density functional theory [2]. Lowest lying structures
are further relaxed utilizing two-component density functional theory taking spin-orbit effects into
account. Simulated beam profiles allow a structural assignment for the most clusters in theexamined range. Neutral lead clusters adopt mainly spherical geometries and resemble thestructures of lead cluster cations apart from Pb10. Inclusion of spin-orbit effects appears crucial fora correct interpretation of the experimental data [3]. Experiments for clusters with more than 18
atoms reveal strong dipole moments for Pb31 and Pb36 and a significantly enhanced polarizability
for Pb25. This points towards unusual geometries for certain cluster sizes although a structural
assignment based on our approach has not been possible yet. Polarizabilities of clusters withmore than 45 atoms are in good agreement with a metallic sphere model taking an electron
spill-out into account.
References[1] D.A. Götz, S. Heiles, R.L. Johnston, and R. Schäfer J. Chem. Phys. 138 (2012) 186101.
[2] S. Heiles, A.J. Logsdail, R. Schäfer, and R.L. Johnston Nanoscale 4 (2012) 1109.
[3] D.A. Götz, A. Shayeghi, R.L. Johnston, P. Schwerdtfeger and R. Schäfer J. Chem. Phys.
140, 164313 (2014)

Structure and thermodynamics

B44

Fabrication of Ag cluster by a novel laser ablation of nanocolloid target
Teppei Nishi, Yusuke Akimoto, Shuji Kajiya, Kosuke Kitazumi, Naoko Takahashi, and Yoshihide
Watanabe
1

TOYOTA CENTRAL R&D LABS., INC. Aichi, Japan

We have developed a novel laser ablation method at air-suspension interface for monodisperse
single nano-sized particle generation in liquid [1]. In this method, the plasma density induced bylaser irradiation is estimated to be low due to the small confined effect of solvent. The collision
probability of excited species produced by laser ablation is small. In our previous study,
micro-sized particles was agitated in a measuring flask filled with pure water by a magnetic stirrer.
Pulsed laser irradiation can induce the fragmentation of target particles agitated in water. It would
be expected that much smaller particles such as sub nano-sized clusters can be fabricated using
smaller target particles. In this paper, we demonstrate a novel method for fabrication of sub
nano-sized Ag cluster by laser ablation at air-suspension interface using Ag nanocolloid target.
Ag nanocolloid target was prepared by laser ablation of Ag powder target precipitated in thebottom of a piriform flask filled with pure water [2]. Second harmonic light from Nd:YAG laser
system (532 nm, 400 mJ/pulse, 10 Hz) was irradiated through the bottom of a piriform flask for 60
minutes. Then, 200 mL of Ag nanocolloid was agitated in a measuring flask by a magnetic stirrer.
Second harmonic light from Nd:YAG laser system (800 mJ/pulse) was focused onto the
air-suspension interface to induce ablation. After laser irradiation for 120 minutes, clear andcolorless colloid could be obtained. The product was analyzed by scanning transmission electron
microscopy (STEM), UV-Vis spectrometry, electrospray ionization mass spectrometry (ESI-MS)
and X-ray photoelectron spectrometry (XPS).
Ag nanocolloid as target showed the surface plasmon absorption around 400 nm. Ag productcolloid after laser ablation at air-suspension interface showed absorption peaks in UV region. It
can be considered that target particles were fragmented by laser irradiation, resulting in sub
nano-sized cluster formation. In addition, STEM and ESI-MS analyses were carried out to confirm
the fragmentation of target particles and fabrication of sub nano-sized particles. These results arecoincident with the consideration from the result of UV-Vis spectrometry.
References[1] T. Nishi, N. Suzuki, N. Takahashi, K. Yano, J. Nanopart Res 15 (2013) 1569.
[2] T. Nishi, H. Sugiyama, N. Suzuki, K. Yano, H. Azuma., J. Photochem. Photobiol. A: Chem 226(2011) 64.

B45

Structure and thermodynamics

Solvation Chemistry of Water-Soluble Thiol-Protected Gold Nanocluster Au102
from DOSY NMR Spectroscopy and DFT Calculations.
Tanja Lahtinen1, Kirsi Salorinne1, Sami Malola2, Jaakko Koivisto1 and Hannu Häkkinen1,2
1

Department of Chemistry, Nanoscience Center, University of Jyväskylä, Finland2

Department of Physics, Nanoscience Center, University of Jyväskylä, Finland

Water-soluble,

thiolatemonolayer-protectedgold

nanoclusters

have

severalbiologicalapplications in microscopy and imaging of biomolecules and bionanoparticles, in drug delivery andin disease targeting [1]. The well-known and characterized water-soluble Au102(pMBA)44 andAu144(pMBA)60 clusters are composed of a metal core and a protecting p-mercaptobenzoic acid(pMBA) ligand layer. However, the clusters become water-soluble only when the carboxylic acidgroup of the pMBA ligand is deprotonated. Hydrodynamic diameter of Aum(pMBA)n [(m,n) =(102,44) and (144,60)] clusters in aqueous media was determined via DOSY NMR spectroscopy[2]. The apparent size of the same (n,m) cluster depends on the counter ion of the deprotonatedpMBA ligand as explained by the competing ion-pair strength and hydrogen bonding interactions
studied in DFT calculations [3].

Scheme 1: Left: A model cluster of Au102(SR)44 built using computationally relaxed pMBA---2H2O---NH4+ complex as a ligand. Right: Schematic presentation of the Aum(pMBA)n clusters as
their sodium salts in aqueous NaOH solution highlighting the effect of sodium counter cation on
the hydrodynamic diameter (----) of the cluster.
References[1] C. J. Ackerson, R. D. Powell and J. F. Hainfeld, Methods Enzymol 48 (2010) 195; V.Marjomäki,
T. Lahtinen, M. Martikainen, J. Koivisto, S. Malola, K. Salorinne, M. Pettersson and
H. Häkkinen, Proc. Natl. Acad. Sci. USA 111 (2014) 1277.
[2] Y. Cohen, L. Avram and L. Frish, Angew. Chem. Int. Ed. 44 (2005) 520.
[3] K. Salorinne, T. Lahtinen, S. Malola, J. Koivisto and H. Häkkinen, Nanoscale 2014,
DOI:10.1039/C4NR01255K.

B46

Structure and thermodynamics

Size-dependent structures of iron oxide cluster ionsstudied by ion mobility mass spectrometry
Tatsuya Komukai, Ryoichi Moriyama, Keijiro Ohshimo, and Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki,
Aoba-ku, Sendai 980-8578, Japan
Iron oxide clusters were recently studied for the purpose of unveiling microscopic properties of thecompounds which are important as semiconductors, magnetic materials, and catalysts. In aprevious study on the structures of neutral iron oxide clusters, (FeO)n [1], stable structures were
two-dimensional (2D) rings for n ≤ 5 and three-dimensional (3D) towers for n ≥ 6. In this study,
we have investigated the structures of (FeO)n+ and FenOn+1+/- cluster ions by ion mobility mass
spectrometry (IM-MS) [2].
Iron oxide cluster ions, generated by reactions between iron vapor formed by laser vaporizationand mixture gas of O2/He in supersonic expansion, were injected into an ion-drift cell by a pulsed
electric field. The cell was filled with He buffer gas with a pressure of 0.90 Torr. An injected ion
reached a constant drift velocity which depends on the collision cross sections between ions and
He atoms. Thus we determined the cross section experimentally from the measured arrival time(and the time that the ion spent in the cell).
Fig. 1 shows the arrival time distributions(ATDs) of (FeO)n+ (n = 4-7) cluster ions. Asn increases, the distributions were shifted tolonger arrival time.

Two Gaussian curves

were necessary for fitting of the ATDs for n ≥5. In order to explain these results, we havecomparedexperimental

andtheoreticalcollision cross sections of cluster ions. As aresult, stable structures of (FeO)n+ were
determined to be 2D rings for n ≤ 5 and 3D
towers for n ≥ 6, as in the previous calculation
results on neutrals.

Therefore, structuralchange from 2D to 3D occurs at around n = 6.
In addition, 2D sheet-like structural isomers
coexist for n ≥ 5. Therefore, the 2D and 3D
structural isomers coexist for n = 6-8. We
will also discuss the structures of FenOn+1+/cluster ions.

Fig. 1. Arrival time distributions of (FeO)n+ (n =4-7). Circles are the observed ion intensities,
and the Gaussian curves show component ofisomers.

[1] N. O. Jones, B. V. Reddy, F. Rasouli, and S. N. Khanna, Phys. Rev. B 72 (2005) 165411.
[2] K. Ohshimo, T. Komukai, R. Moriyama, and F. Misaizu, J. Phys. Chem. A 118 (2014) 3899.

B47

Structure and thermodynamics

Fabrication of Rh nanoframes through dissolution of Au cores of Au@Rh
core-shell nanorods by the addition of HCl
Yukinori Nakashima,1 Masashi Hattori,2 and Masaharu Tsuji2
1

Department of Applied Science for Electronics and Materials, Kyushu University, Kasuga, Japan
2

Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Japan

Many interesting static and dynamic properties of nanoparticles that cannot be observed in bulk
metals have been reported. Among them, nanoparticles of platinum group, such as Pt, Pd, and Rh,
were widely used as environmental catalysts for NOx removal. However，nanoparticles of these Ptgroup are expensive. Therefore, reduction of use of Pt group nanoparticles is expected.
Nanoframes having hollow interior structures are expected to have high catalytic activity, because
specific surface area of nanoframes is larger than that of normal spherical nanoparticles. In thisstudy, we attempt fabrication of nanoframes of Rh particles using a unique procedure. Rh
nanoframes were prepared by synthesis of Au@Rh core-shell nanorods (NRs) followed by theselective etching of Au NR cores by addition of HCl in an aqueous solution.
In the first step Au@Rh core-shell NRs were prepared by heating a mixture of Au NRs, hexadecyl
trimethyl ammonium bromide, ascorbic acid, and rhodium chloride in an aqueous solution in an oilbath at 95 oC for 3 h. TEM and TEM-energy dispersive X-ray spectrometry (EDS) images of
products are shown in Figs. 1(a) and 1(c). Results show that Au NR seeds are covered by Rh
shells. Rh shells consist of small particles because Rh shells are not formed via layered growth but
they are produced via island growth owing to large lattice mismatch between Au and Rh (6.9%).
In the second step, 5 % hydrochloric acid wasadded to Au@Rh core-shell solution and heated in

(a)

(b)

an oil bath at 95 oC for 12 h. TEM and TEM-EDS of
products are shown in Figs. 1(b) and 1(d). It isclear from Fig. 1(b) that hollow nanoframes areformed. When Au:Rh atomic ratio over this image
was evaluated from TEM-EDS image, it was 1：9.

50 nm
(c)

50 nm
Au

(d)

Rh

This suggests that Rh-rich nanoframes were

Rh
Au
Rh

Au
Rh

produced in the second step. Rh nanoframes haveconcave-convex shapes because Rh shells of
precursor Au@Rh core-shell nanoparticles consistof small island-type particles. These small Rh
particles remain after dissolution of Au NRs andform nanoframe shapes.

50 nm

nm Au@Rh
50 nm
Figure1．TEM images of50(a)NRs and (b) Rh nanoframes. TEM-EDS
images of (c) Au@Rh NRs and (d) Rh
nanoframes.
50 nm

B48

Structure and thermodynamics

Effect of Core Size on Au-Pt Core-Shell Nanoparticles
for Oxygen Reduction Reaction
Saki Hirose,1 Yoshikiyo Hatakeyama,2 Ken Judai,2 Takeshi Morita,1 and Keiko Nishikawa1
1

Graduate School of Advanced Integration Science, Chiba University, Chiba, Japan
2

College of Humanities and Sciences, Nihon University, Tokyo, Japan

Au-Pt core-shell nanoparticles are attractive materials for reduction of the Pt usage. The core-shell
nanoparticles show the higher catalytic activities for oxygen reduction reaction (ORR) compared tocommercial Pt/C.[1] It is also reported that the particles with small Au-cores have higher durability
than with large cores.[2] Method of regulation of the catalytic activity by the core-size will beapplied to other combination of metals and wide reaction system. Four groups of Au nanoparticles(AuNPs) were prepared for the present study.
The AuNPs were synthesized in an ionic liquid by sputter depositionof Au.[3] The sizes of AuNPs were controlled by temperature of theionic liquid.[4] Four groups of AuNPs with different sizes weresynthesizedin

1-butyl-3-methylimidazolium

tetrafluoroborate([C4mim]BF4, Fig. 1). The AuNPs-supported carbon blacks (Au/CB)
were obtained by mixing AuNPs containing ionic liquids with CB. Pt

Fig. 1 Chemical structure of[C4mim]BF4.

shells were formed by spontaneous reduction of K2PtCl4 on the surface of AuNPs (Au-Pt/CB).[5]The effect of Pt-shell formation in size of thenanoparticles was investigated by small-angle X-ray
scattering (SAXS). The catalytic activities werecharacterized by electrochemical measurements. Fig.
2 shows the size distribution of Au/CB and Au-Pt/CB.
The size slightly increased after the formation of Pt
shells. It is thought that increase of the size is causedby reduction and deposition of Pt onto the surface of
AuNPs. The same tendency was observed for other
Au-Pt/CBs with different core sizes. Hydrogen
adsorption-desorption waves are confirmed by cyclic
voltammetry after Pt shell formation. In addition to theresults, we will discuss ORR activity of Au-Pt/CB in
HClO4 aq.

Fig. 2 The size distribution of
the formed nanoparticles.

References[1] X. Li, J. Liu, W. He, Q. Huang, and H. Yang, J. Colloid. Interf. Sci., 344, (2010) 132.
[2] Inaba et al., ECS Transactions, 33, 1, (2010) 231.
[3] Torimoto et al., Appl. Phys. Lett., 89, (2006) 243117.
[4] Y. Hatakeyama, S. Takahashi, and K. Nishikawa, J. Phys. Chem. C, 114, (2010) 11098 .
[5] Tsuji et al., The 218th ECS Meeting, Abstract #858 (2010)

Structure and thermodynamics

B49

Melting of Weakly-Bound Systems by Monte Carlo Simulations –Applications to Mercury and Argon under High Pressure
Elke Pahl,1 Jonas Wiebke1, Peter Schwerdtfeger1and Florent Calvo2
1

Centre of Theoretical Chemistry and Physics, Institute for Natural and Mathematical Sciences
and The New Zealand Institute for Advanced Study, Massey University Auckland
2

ILM, UMR 5306, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex

Our goal is to understand the melting of weakly-bound systems based on parallel tempering Monte
Carlo (MC) simulations which are based on highly accurate ab initio models for the interactionenergy of the N-atomic system. I will present results 1) on the explanation of the exceptionally low
melting temperature of mercury, Hg [1] and 2) on high-pressure melting of Argon up to pressuresof 100 GPa [2].
Mercury is the only elemental metal liquid at room temperature, a fact that puzzled chemists for along time. We were able to show that this melting point depression is caused by an interplay of
scalar-relativistic and complicated many-body effects. Herefore, the many-body effects were
described in an efficient way within the so-called diatomics-in-molecules (DIM) formalism [3] and a
non-relativistic version of the DIM model was developed [4]. Both models were updated by using
highly accurate, ab initio ground and excited potential curves of the Hg dimer [5]. While the results
for small clusters are not following a well-defined trend with increasing cluster size, we get very
convincing results for the extended system - within the relativistic model, the experimental melting
temperature as well as the density is very well reproduced. And a comparison with the
non-relativistic results proves without doubt the impact of relativity: Without relativistic effects
mercury would melt more than 100°C higher than observed and would not be liquid at room
temperature [1]!
For the high-pressure melting studies our MC code has been extended from canonical ensembles
to isobaric, isothermal ensembles. Results for the melting of solid Argon under high pressures of
1-100 GPa are found to be very accurate and probably exceeding experimental accuracy [2], after
effects of ‘super-heating’ in the simulations are accounted for.
References[1] F.Calvo, E.Pahl, M.Wormit, P.Schwerdtfeger, Angew.Chem.Int.Ed. 17 (2013) 7583–7585.
[2] J.Wiebke, E.Pahl, P. Schwerdtfeger, Angew. Chem. Int. Ed. 52 (2013), 13202-13205.
[3] H. Kitamura, Chem. Phys. 325 (2006) 207–219.
[4] F. Calvo, E. Pahl, P. Schwerdtfeger, F. Spiegelman, J. Chem. Theory Comput. 8 (2012)
639–648.
[5] E. Pahl, D. Figgen, C. Thierfelder, K. A. Peterson, F. Calvo, P. Schwerdtfeger, J. Chem. Phys.
132 (2010)

Structure and thermodynamics

B50

Design of Three-shell Icosahedral Matryoshka Clusters A@B12@A20 (A = Sn, Pb;
B = Mg, Zn, Cd, Mn) Including a New Type of Magnetic Superatoms
Xiaoming Huang 1, Jijun Zhao *1,2, Yan Su 1, Zhongfang Chen 3, R. Bruce King *4
1

Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University ofTechnology), Ministry of Education, Dalian 116024, China.
2

3

Beijing Computational Science Research Center, Beijing 100089, China.

Department of Chemistry, Institute for Functional Nanomaterials, University of Puerto Rico, San
Juan, PR 00923, USA.

4

Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens,
Georgia, USA.

We propose a series of icosahedral matryoshka clusters of A@B12@A20 (A = Sn, Pb; B = Mg, Zn,
Cd), which are thermodynamically and chemically stable with large HOMO-LUMO gaps (1.29 to
1.54 eV) and low formation energies (0.06 to 0.21 eV/atom). A global minimum search using a
genetic algorithm and density functional theory calculations confirms that such three-shellonion-like structures are the ground states for these A21B12 binary clusters. All of these icosahedral
matryoshka clusters, including two previously found ones, i.e., [As@Ni12@As20]3– and[Sn@Cu12@Sn20]12–, follow the 108-electron rule, which originates from the high Ih symmetry andconsequently the splitting of superatom orbitals of high angular momentum (1H and 1I). Moreinterestingly, two magnetic matryoshka clusters, i.e., Sn@Mn12@Sn20 and Pb@Mn12@Pb20, aredesigned, which combine a large magnetic moment of 28 µB, a moderate HOMO-LUMO gap, andweak inter-cluster interaction energy, making them ideal building blocks in novel magnetic
materials and devices.

Structure and thermodynamics

B51

Structures, electronic and magnetic properties of Fe2Gen- and Cr2Gen- (n=3-12)
clusters from DFT calculations and photoelectron spectra
Xiaoqing Liang1, Xiaoming Huang1, Jijun Zhao1*, Hongguang Xu2, Weijun Zheng2
1

State Key Laboratory of Materials Modification by Laser, Electron, and Ion Beams, Dalian
University of Technology, Ministry of Education, Dalian 116024, China
2
Beijing National Laboratory for Molecular Science, State Key Laboratory of Molecular Reaction
Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Transition metal doped semiconductor clusters (such as silicon and germanium clusters) havebeen focus of intensive studies during the last decade. Until now, most efforts have devoted to
semiconductor clusters doped with single transition metal atom. Combining spin-polarized density
functional theory (DFT) and photoelectron spectroscopy, the growth behavior, electronic andmagnetic properties of Fe2Gen- and Cr2Gen- (n=3-12) clusters have been investigated. A genetic
algorithm incorporated with DFT optimization has been employed to globally search the groundstate configurations. The theoretical photoelectron spectra are in good agreement with ourexperimental ones. In the lowest-energy structures, one Fe or Cr atom tends to stay in the interiorsite from n=8. The local magnetic moments on the two Fe atoms in Fe2Gen- clusters exhibit
ferromagnetic ordering. In contrast, the spin moments on two Cr atoms in Cr2Gen clusters show
antiferromagnetism or ferrimagnetism. Interestingly, the magnetic moments of two Fe atoms and Cr
atoms do not change sensitively with cluster size.

Structure and thermodynamics

B52

Geometric, electronic, and magnetic structure of FexOy clusters
Remko Logemann,1 Gilles de Wijs, 1 Mikhail Katsnelson1 and Andrei Kirilyuk1
1

Institute for Molecules and Materials, Radboud University Nijmegen, Nijmegen, The Netherlands

Atomic clusters are a promising model system to study the emergence of bulk physical properties
at the nanoscale and below. For example for transition metal oxides, the photoelectron spectra of
FexOy- clusters have been used to model the chemisorption of oxygen on iron [1]. Furthermore themagic Fe13O8 was extensively studied as a model system to understand the iron oxide interaction[2]. In addition to these studies, we propose FexOy as a model system to study the fundamental
magnetic interactions. As a starting point, a detailed understanding of the relation between thegeometry and electronic structure of these clusters is required.
Here we combine Density Functional Theory (DFT) calculations with infrared vibration
spectroscopy data [3] to understand the structural, electronic and magnetic properties ofgas-phase FexOy+/0 clusters. First, possible geometric structures were identified using a genetic
algorithm. They were further geometrically optimized for all magnetic states using the hybrid
B3LYP functional [4]. For the lowest-energy structures the vibration spectra are calculated. For
unambiguous identification of the cluster structures these were compared with the experimentallymeasured resonant dissociation spectra of the cluster-messenger [3].
The magnetic structures of FexOy+/0 clusters contain both pure antiferromagnets as well as
ferrimagnets where a magnetic moment is present due to the odd number of Fe atoms. The
electronic structure of these clusters is compared with calculations on bulk magnetite. In the latter,both Fe2+ and Fe3+ atoms are present so that the valence state of Fe in the clusters is also
considered and compared to the bulk. It turns out Fe3O4, Fe4O6 are monovalent, whereas Fe4O5
and Fe5O7 have mixed valence states. Note that the calculations of the magnetic configurations
were done both with the B3LYP functional mentioned above, and with the GGA+U approach [5].
The parameter U was derived by comparing the calculated electronic structures, and happened to
be of the same order as for the bulk iron oxides.
References[1] L.S. Wang, H. Wu, and S.R. Desai, Phys. Rev. Lett. 76, 4853 (1996)[2] Q. Wang, Q. Sun, M. Sakurai, J.Z. Yu, B.L. Gu, K. Sumiyama, and Y. Kawazoe, Phys. Rev. B
59, 12672 (1999)[3] A. Kirilyuk, A. Fielicke, K. Demyk, G. von Helden, G. Meijer, and Th. Rasing, Phys. Rev. B 82,
020405(R) (2010)[4] A.D. Becke, J. Chem. Phys. 98, 5648 (1993)[5] A.I. Liechtenstein, V.I. Anisimov, and J. Zaanen, Phys. Rev. B 52, R5467 (1995).

B53

Structure and thermodynamics

Redispersibility of Solid State Cysteine-Capped CdSe Nanoparticles
Depending on pH Values of These Aqueous Solution
Takuya Kurihara, Yasuto Noda, and K. Takegoshi
Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto, Japan
It is important for studies and applications of nanoparticles (NPs) synthesized in solvents to keep
their properties after solidification. In this study, we show that the redispersibility of powder
cysteine-capped CdSe NPs (CdSe-Cys) depends on pH values of CdSe-Cys aq. in solidifying, andelucidate the dependency by using solid state NMR.
Powder CdSe-Cys were synthesized by means of a method to be presented elsewhere in theconference by the authors. Then they were redispersed into cysteine aq. with pH 11 and 9 andsolidified by adding acetone as antisolvent. Each powder is referred below as CdSe-11 and -9.
CdSe-11 showed water redispersibility, while CdSe-9 could not be redispersed well.
Figure 1 shows 13C{1H} CP/MAS NMR spectra of CdSe-11 (a) and CdSe-9 (b). The peaks shownin Fig.1(a) are assigned as follows : the peak at 33 ppm is 13C bonding to sulfur, at 54~59 ppm arebonding to amine, and at 181 ppm is of carboxy group. While in Fig.1(b), the peak at 181 ppm isfairly week, and a new peak appears at 174 ppm.
Abraham et al. reported a 13C solid state NMR peak+of carboxy groups of cysteines forming COO -NH3(a)ion complex between ligand- and free-cysteines at
173 ppm[1,2]. The pH 9, adjusted in solidifying
CdSe-9, is lower than pKaNH2 10.8 of cysteine, thus+

many amines become NH3 and they are likely to-form ionic bonds with COO by solidification. Thus
this peak would be assigned as

(b)

13

C of carboxy

group of cysteine forming the same ionic bonds
betweenligand-cysteines

andligand-and/orfree-cysteines. Therefore, the reason why CdSe-9
cannot redisperse should be the formation of ionicbonds between cysteines which disturb hydration.

200

180 160 140 120 100
13References

80

60

40

20

0

Chemical Shift/ppm

Figure 1
C NMR spectra of (a) CdSe-11 and(b) CdSe-9, measured with a 1 ms contact time.

[1] A. Abraham et al., J. Phys. Chem. C, 114 (2010), 18109.
[2] A. Abraham et al., J. Phys. Chem. B, 116 (2012), 7771.

This work is supported by JSPS KAKENHI Grant Number 25888009.

Structure and thermodynamics

B54

Structural Stability in icosahedral Ni-Zr-Nb ternary clusters
Nobuhisa Fujima,1 Toshiharu Hoshino,1 and Mikio Fukuhara 2
1

Department of Electronics & Material Science, Shizuoka University, Hamamatsu, Japan2

New Industry Creation Hatchery Center, Tohoku University, Sendai, Japan

Interesting electronic transport phenomena, superior (ballistic) conducting and superconducting
transport, and electric current-induced voltage (Coulomb) oscillation, have been observed in
Ni-Zr-Nb-H amorphous alloys, ((Ni0.6Nb0.4)1−xZrx)100−y Hy (0.3 ≤ x ≤ 0.5, 0 ≤ y≤ 20). Local atomic
structures (icosahedral clusters and their surroundings) in the alloys play an important role ingeneration of these phenomena.
We optimize the atomic structures of icosahedral Ni4Zr6Nb3 clusters by the first principles
calculation, with twenty energetically inequivalent initial atomic positions, where a Ni tetrahedron is
includes as a core cluster.[1] Figure 1 shows the total energies of the twenty optimized clusters
as a function of Nb-Ni coordination number and two optimized structures with the maximal (1) andminimal (2) energies. We find that all the optimized clusters remain in the (distorted) icosahedral
structures as shown in the two examples, and that the total energy almost linearly depends on the
Nb-Ni coordination number. These results suggest that the Nb atoms and their clustering isolated
from Ni atoms stabilize the icosahedral structure and prevent the local structure from crystallizing
to other phases (fcc-like ordered phase etc.).

Fig.1 Nb-Ni coordination number dependence in total energy of Ni4Zr6Nb3 icosahedral clusters andoptimized structures of two clusters (1) and (2).
Reference[1] N. Fujima, T. Hoshino, and M. Fukuhara, J. Appl. Phys. 114 (2013) 063501.

B55

Structure and thermodynamics

Synthesis of Porphyrin-face Coordinated Au Clusters and Their Interfacial
Interaction
Masanori Sakamoto,1,2 Daichi Eguchi,1 and Toshiharu Teranishi1
1

Institute for Chemical Research, Kyoto University, Japan
2

PRESTO-JST, JapanFor the organic molecules/Au clusters (AuCs) composites system, interfacial interaction between
Au and π-conjugated molecule is an important subject from the viewpoint of scientific interest as
well as the application for nanoelectronic devices. In the present research, we synthesized AuC
face-coordinated by porphyrin derivatives and investigated their interfacial interactions.
We synthesized porphyrin derivatives contain four acetylthio groups (i.e., binding sites to the AuC)
facing the same direction toward the porphyrin ring (SCnP, n = 0 ~ 2) (Fig.1) [1],[2]. This led to aface-on configuration for the porphyrin on the AuCs through quadridentate coordination. The SC0P
binding sites are directly connected to the meso-substituted phenyl groups while SC1P and SC2P
contain methylene spacers (i.e., distances between the porphyrin ring and the sulfur atoms were
~2.6, ~3.4 and 4.85 Å for SC0P, SC1P and SC2P, respectively). The structure of theporphyrin-coordinated AuC was characterized by atomic resolution high-angle annular dark fieldscanning transmission electron microscopy, MALDI-TOF-MS, and inductively coupled plasma
atomic emission spectroscopy. The interaction between the porphyrin and the AuCs wasinvestigated by UV-vis-NIR and transient absorption (TA) measurements. Interestingly,
UV-vis-NIR spectra indicated the strong interfacial interaction between porphyrin and AuC
depending on the distance between porphyrin and AuC (Fig.1b). TA measurement revealed theexciplex formation between AuC and porphyrin ring (Fig.1c)[2].
Oa)c) 0.020b) 4.0

S
()
n

0.015

( )n S

( )n
S
O

O

O.D.

H
N

-1

N

N

0.010

SC2P-AuCs-1

NH

S ( )n2.0

SC0P-AuCs

5O

ε (×10 M cm )

3.0

0.005
0.000
-0.005

SC1P-AuCs

1.0

1.5 ps
3 ps
30 ps-0.010-0.015n = 0 : SC0P
n = 1 : SC1P
n = 2 : SC2P

0.0

-0.020

400

500
600
Wavelength (nm)

700

800

600

700

800

900

1000

1100

1200

Wavelength (nm)Fig.1 a) structure of porphyrin derivatives ((SCnP, n = 0 ~ 2)), b) UV-vis-NIR absorption spectra of
SCnP-coodinated AuC, c) TA spectra of SC0P-coodinated AuC.
References[1] M. Sakamoto, D. Tanaka, H. Tsunoyama, T. Tsukuda, Y. Minagawa, and Y. Majima, T.
Teranishi, J. Am. Chem. Soc. 134 (2012) 816.
[2] D. Tanaka, Y. Inuta, M. Sakamoto, A. Furube, M. Haruta, Y.-G. So, K. Kimoto, I. Hamada, andT. Teranishi, Chem. Sci. 5 (2014) 2007.

Structure and thermodynamics

B56

Origin of Magic Stability for Aluminum-Boron Binary Nanoclusters
Tomomi Nagase,1 Shoichiro Suga,1 Hironori Tsunoyama,1,2 and Atsushi Nakajima1,2
1

Department of Chemistry, Keio University, Japan
Nakajima Designer Nanocluster Assembly Project, JST-ERATO, Japan2

The physical and chemical properties of nanoclusters (NCs), which differ from the bulk, are uniqueand highly size dependent.1 Based on extensive experimental and theoretical studies of aluminum(Al) NC anions,2-7 Al13- and Al23- NC anions show superior stability toward etching reaction bymolecular oxygen attributable to their closed electronic structures. It has been suggested fromelectronic structure that doping of boron (B) atoms to Al NC anions enhances the stability of Al-B
binary NC anions by replacement of interior Al atoms with smaller B atoms with keeping their total
valence electrons.8 In contrast to extensive studies for small Al and Al-B NCs (smaller than
23-mer), studies for larger magic NCs have been still limited probably because of difficulty in thegeneration of such NCs by a laser vaporization method, although larger magic numbers havebeen proposed.3 In the present study, we have investigated the magic number and composition of
Al-B binary NC anions (AlnBm-) larger than 23-mer by a magnetron type NC source combined withreaction toward molecular oxygen. We have found that all of NCs with n+m=37 showed the locallymaximized stability irrespective of different numbers of B atoms (m=0-6), whereas magic
compositions (n/m) appeared for 13- and 23-mer NCs as Al12B1- and Al21B2-. The result suggeststhat the origin of stability changes from concerted electronic-geometric factors for 13 and 23-merto the electronic shell closing for 37-mer.
Al-B binary NCs were generated by magnetron sputtering-gas condensation apparatus.9 At
downstream of the NC source, NC ions were reacted with oxygen molecules (O2) introduced as
effusive beam perpendicular to the NC beam. The reactivity of individual NCs was analyzed byquantitative comparison of mass spectra before and after the O2 exposure; the reaction with O2
decreased the intensity of NC ions without the formation of oxygen adducts, AlnO- and AlnO2-.
The series of AlnBm- [(n,m), 5<n<50, m = 0–6] binary NC anions were observed as smooth
distribution without prominent magic numbers at n+m=13 and 23 in the mass spectrum without theO2 introduction. After the reaction with O2, a series of NC ions with total atoms of 37, (37–m, m)(m=0–6), along with known magic NCs of n+m=13 and 23 were prominently observed. For 13- and23-mer NCs, the reactivity dramatically increases from (12,1) to (11,2) and (21,2) to (20,3),
respectively. In contrast, the intensities of (32,5) and (31,6) were relatively strongly observed thanthe other neighboring ions, although these ions were overlapped with (34,0) and (33,1) in themass spectrum, respectively. Note that (34,0) and (33,1) were not strongly observed without theoverlapped formation of (n, m)=(32,5) and (31,6) NCs. A spherical harmonic potential3 predicts
electronic stability for 13-, 23-, and 37-mer owing to the electronic shell closing. Therefore, we
conclude that the stability of 37-mer results mainly from the electron shell closing, whereas thestabilities of 13- and 23-mer are attributed to both of electronic and geometric factors. In otherwords, the origin of the stability changes from 23 to 37 atoms; concerted electronic-geometricfactors dominates the stability below 23-mer, whereas the electronic factor becomes predominant
above 37-mer.
References[1] R. L. Johnston, “Atomic & Molecular Clusters”. [2] R.E. Leuchtner et al., J. Chem. Phys. 91(1989) 2753. [3] X. Li et al., Phys. Rev. Lett. 81 (1998) 1909. [4] A. Nakajima et al., Chem. Phys.
Lett. 187 (1991) 239. [5] L. Ma et al., J. Chem. Phys. 132 (2010) 104303. [6] T. Iwasa et al., Chem.
Phys. Lett. 582 (2013) 100. [7] T. Watanabe et al., J. Chem. Phys. 117 (2013) 6664. [8] H.
Kawamata et al., Chem. Phys. Lett. 337 (2001) 255. [9] H. Tsunoyama et al., Chem. Lett. 42(2013) 857.

B57

Structure and thermodynamics

Geometrical structures of vanadium oxide cluster ionsstudied by ion mobility mass spectrometry
Ryoichi Moriyama, Jenna W. J. Wu, Hiroshi Tahara, Keijiro Ohshimo, and Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki,
Aoba-ku, Sendai 980-8578, Japan
Neutral and ion structures of vanadium oxide clusters VmOn+/0/- have been taken much interest as
microscopic models of bulk V2O5 catalyst surface. For neutral (V2O5) m/2 clusters up to m = 24,
polyhedron structures were suggested by DFT calculations [1].

The vibrational spectra andphotodissociation reactions of small sized cluster ions (m < 10) were also measured, and theresults were compared with theoretical predictions [2].

In the present study, collision crosssections (CCSs) of the vanadium oxide cluster ions were measured by ion mobility mass
spectrometry.

By comparing the experimental CCSs with theoretical ones, geometricalstructures were determined.
VmOn+/- ions were injected into a drift cell with a pulsed electric field, after generation by laser
vaporization with 5 % O2-mixed He gas in supersonic expansion. In the drift cell, ions collided
with He buffer gas under an electrostatic field and reached a constant drift velocity, which depends
on the CCS of the ions with He. Experimental CCSs of the ions could be estimated from the timethat ions spent in the cell. Theoretical CCSs were independently calculated using the projection
approximation method in MOBCAL program, for the structures optimized by B3LYP/6-311+G(d)level.
Most abundant cluster ions were dependent on parity of the number of vanadium atoms m;(V2O5)m/2+ for even m and (VO2)(V2O5) (m-1)/2+ for odd m [3]. CCSs of these ions up to m = 60 were
measured as shown in Fig.1. Experimental CCSs increase uniformly with cluster size, which
follows a rule for three dimensional cluster
growth, CCS ∝ (mass number)2/3. The trendof the calculated CCSs of prism structures foreven m up to m = 10 agreed well withexperimental data. For odd sized ions (m = 7
and 9), quasi-prism structures were in good
agreement

withexperiment.

These

quasi-prism structures have one tricoordinatedoxygen atom which can also be found in bulk
V2O5 crystals.

Fig.1 Experimental (m = 2-60) and theoretical+(m = 2-10) CCSs of VmOn .

References[1] S. F. Vyboishchikov, and J. Sauer, J. Phys. Chem. A 105 (2001) 8588.
[2] G. Satambrogio, M. Brümmer, L. Wöste, J. Döbler, M. Sierka, J. Sauer, G. Meijer, and K. R.
Asmis, Phys. Chem. Chem. Phys 10 (2008) 3992.
[3] J. W. J. Wu et al., ISSPICXVII. Poster.

B58

Structure and thermodynamics

Synthesis of stable gold clusters face-coordinated by porphyrin derivatives
containing disulfide groups
Daichi Eguchi,1 Masanori Sakamoto,1,2 and Toshiharu Teranishi1
1

Institute for Chemical Research, Kyoto University, Uji, Japan
2

JST-PRESTO, Japan

Stability of gold clusters (AuCs) is an important aspect for applications, such as catalysis,
biosensors, and nanoelectronics. Our groups have recently synthesized the porphyrin
face-coordinated AuCs [1,2]. However, the instability of porphyrin face-coordinated AuCs has
been an obstacle for applications. In this study, we have synthesized quite stable AuCs
coordinated by porphyrin derivatives with disulfide groups and investigated their properties as well
as stability.
Wesynthesizedtheporphyrin

derivative:

5α,10α-bis(2-ethylthiophenyl)-15α,20α-bis(2’-ehylthiophenyl)porphyrinatozinc ( Ⅱ ) (ZnSC2P-SS, Fig 1). The ZnSC2P-SS contains two
disulfide groups facing in the same direction to the porphyrin ring, which bind to the AuCs in aface-coordination fashion. The AuCs coordinated by the ZnSC2P-SS (ZnSC2P-SS-AuCs) weresynthesized by the reduction of the Au(Ⅲ) ions in the presence of ZnSC2P-SS. The purification of
the obtained ZnSC2P-SS-AuCs was performed by gel permeation chromatography.
The size of the ZnSC2P-SS-AuCs were measured by TEM. ZnSC2P-SS-AuCs have the size of 1.5±0.1 nm (Fig. 2), and are thought to possess the platonic hexahedral structure, as shown in Fig. 3[1]. This result agrees well with the AuCs coordinated by the porphyrin with acetylthio groups,
reported in the previous work [1]. ZnSC2P-SS-AuCs showed higher stability than the previous
ones in ambient conditions. Furthermore, we will report the electronic, optical, catalytic properties
of ZnSC2P-SS-AuCs.

References[1] M. Sakamoto, D. Tanaka, H. Tsunoyama, T. Tsukuda, Y. Majima, and T. Teranishi, J. Am.
Chem. Soc. vol 134 (2012) 816.
[2] D. Tanaka, Y. Inuta, M. Sakamoto, A. Furube, M. Haruta, Y.-G. So, K. Kimoto, I. Hamada, andT. Teranishi, Chem. Sci. vol 5 (2014) 2007.

B59

Structure and thermodynamics

Observation of halogen adsorbates on magic numbered gold clusters stabilized
by polyvinylpyrrolidone
Setsuka Arii,1 Satoru Muramatsu,1 Seiji Yamazoe,1, 2 Kiichirou Koyasu,1, 2 and Tatsuya Tsukuda1, 2
1

Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
2

ESICB, Kyoto University, Kyoto, Japan

Small (< 3 nm) gold clusters stabilized by polyvinylpyrrolidone (Au:PVP) show size-specificcatalysis for aerobic oxidation of alcohols [1]. In contrast to the generally accepted model that bare
Au clusters were stabilized by PVP, we observed for the first time a series of halogen adsorbates
on Au clusters by MALDI mass spectrometry. We also found that these halides affect theelectronic structures and catalysis of Au:PVP.
Au:PVP(X) (X = Cl, Br) with the average diameter of around 1 nm were synthesized by reductionof AuX4— in the presence of PVP and deionized by ultrafiltation as previously reported [2]. MALDI
mass spectra of Au:PVP(X) were recorded under minimal laser power to suppress laser-induced
fragmentation. Halogenated gold clusters AunXm—(X = Cl, Br) with n = 24, 34, 43 were observed ashighly abundant species regardless of the halogen (Fig. 1). Interestingly, the numbers of Br
adsorbed were larger than those of Cl (Fig. 2).
The effect of halogen adsorbates on the electronic structures of the Au clusters was examined by
XPS and XANES. It was demonstrated that Au clusters in Au:PVP(Br) were more negatively
charged than those in Au:PVP(Cl). Nevertheless, Au:PVP(Br) showed poorer catalytic activity foralcohol oxidation than Au:PVP(Cl). This result suggests that adsorbed halogens retard thecatalysis of Au clusters by steric constraint.

Fig.1 Typical MALDI mass spectra o Au:PVP(Cl)

Fig.2 Distribution of number of adsorbed
halogen atoms

References[1] H. Tsunoyama, H. Sakurai, and T. Tsukuda, Chem. Phys. Lett. 429 (2006) 528.
[2] H. Tsunoyama, H. Sakurai, Y. Negishi, and T. Tsukuda, J. Am. Chem. Soc. 127 (2005) 9734.

B60

Structure and thermodynamics

Secondary ion emission from micro droplets induced by fast ion impacts
Takuya Majima,1 Tatsuya Nishio,2 Kensei Kitajima,2 Yoshiki Oonishi, 2Hiroki Ueda, 2 Hidetsugu Tsuchida,1 and Akio Itoh1,21Quantum Science and Engineering Center, Kyoto University, Kyoto, Japan2

Department of Nuclear Engineering, Kyoto University, Kyoto, Japan

To investigate radiation-induced molecular processes in liquids, we have developed a newexperimental system for analyzing secondary ions emitted from micro droplets in MeV-energy ion
collisions. Conventional experiments of swift ion interaction with liquid targets were performed
under atmospheric pressure because of high vapor pressure of liquid targets. Accordingly,
analyzing methods of reaction products is limited to spectroscopic or chemical studies. In this work,
we performed fast ion irradiation of liquid droplets in vacuum by employing a droplet beamtechnique [1]. This allows us to apply mass spectrometric techniques for product ions emitted fromdroplet surfaces in fast ion impacts.
The experiment was performed at a 2MV tandem type Pelletron accelerator at Quantum Science
Engineering Center, Kyoto University. Micro droplets of water and ethanol were injected into a
vacuum chamber and crossed with 0.7–2.0 MeV H+ and 2.0 MeV C2+ ion beams from theaccelerator. The droplet diameter was
estimated to be a range of few μm byanalyzing energy loss distributions of
H+ ions after penetrating through the
droplets.

Positiveandnegativesecondary ions from the droplets incollisions with 2.0 MeV C2+ ions wereanalyzed by a time-of-flight mass
spectrometer. Figure 1 shows anexample of mass spectra of negative
secondary ions from water droplets,

Figure 1. Mass spectrum of negative secondary ionsexhibiting emission of cluster ionsfrom water droplets induced by 2.0 MeV C2+.

-

(H2O)nOH up to about n ~ 15.
We gratefully acknowledge Dr. J. Kohno for his advice on the liquid droplet technique. One of theauthors (T.M.) would like to acknowledge the support of Toyota Physical & Chemical ResearchInstitute Scholars.
Reference[1] J. Kohno, N. Toyama, T. Kondow, Chem. Phys. Lett. 420 (2006) 146.

Structure and thermodynamics

B61

Drift time measurements of H3O+ hydrate formed by NO+ injection into drift tube
filled with H2O/buffer gas at low temperatures
Hiroshi Hidaka,1 Yoichi Nakai,2 Takao M. Kojima3, and Naoki Watanabe1
12Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, JapanRIKEN Nishina Center for Accelerator-Based Science, Wako, Saitama 351-1098, Japan
3

Atomic Physics Laboratory, RIKEN, Wako, Saitama 351-0198, Japan

H3O+ hydrate, H3O+(H2O)n, is known to exist in the terrestrial ionosphere in quantities. As one of
the important formation-pathways, H3O+(H2O)n formation via NO+(H2O)m:NO+(H2O)m + H2O → H3O+(H2O)m-1 + HONO (m=3,4),
has been often proposed and indeed studied in flow-tube experiments[1,2]. However, in thoseexperiments, the parent NO+ ions were produced by conventional electron impact method andthus contained the metastable NO+. Since the ionization energy to the lowest metastable state of
NO+(a3∑+) is 15.66eV[3], H2O in the ground state having the ionization energy of 12.65 eV can be
ionized by the charge exchange with the metastable NO+ ions. If the charge-exchange reaction
occurs, the new formation pathway of H3O+(H2O)n may open as follows:
H2O + NO+( a3∑+)→ H2O+ + NO,
H2O+ + H2O → H3O+ + OH,
H3O+ + H2O + M → H3O+(H2O) + M,
H3O+(H2O)n-1 + H2O + M → H3O+(H2O)n + M.
The above processes are not appropriate in atmospheric environments. Therefore, in order tostudy the formation pathway of H3O+(H2O)n via NO+(H2O)m alone, the formation of H3O+(H2O)nthrough the charge-exchange reaction must be separated in the experiment.
Using a newly-developed ion drift-tube with selected-ion injection, we tried to separate thecontribution of metastable NO+ on the H3O+(H2O)n formation. In our experiment, the NO+ beamincluding the metastable NO+ was injected in the H2O-filled drift-tube and the products of
H3O+(H2O)n were analyzed in the back of the tube. The drift time for the products in the tube
provides the information of products’ origins. That is, when measuring the drift-time spectrum of
H3O+(H2O)n, the spectrum consists of two peaks depending on the different origins, NO+(H2O)m or
H2O+ from the metastable NO+.
Reference(s)[1] N. Eyet, et al., J. Phys. Chem. A 115 (2011) 7582.
[2] F. C. Fehsenfeld et al., J. Chem. Phys. 55 (1971) 2120.
[3] D. L. Albritton, et al., J. Chem. Phys. 71 (1979) 3271.

B62

Structure and thermodynamics

Solid-state absorption properties and crystal structures of di-alkynylated
octanuclear gold clusters
Mizuho Sugiuchi,1 Naoki Kobayashi,1 Yukatsu Shichibu,1,2 and Katsuaki Konishi1,21Graduate School of Environmental Science, Hokkaido University, Sapporo, Japan
2
Faculty of Environmental Earth Science, Hokkaido University, Sapporo, Japan

In contrast to conventional monophosphine-ligated gold clusters showing similar optical profiles
with each other,[1] we found that diphosphine-ligated gold clusters showed unique prolate
geometries and unusual absorptions.[2-4] Among them, octanuclear clusters had some interesting
properties such as redox-activated core-shape transformation involving photoluminescencechange and selective emission turn-off against Hg (II).[4] Furthermore, di-alkynylations of one ofthe octanuclear clusters and protonation-responsive chromisms of the pyridylethynyl-substitutedclusters in solution were demonstrated.[5] In this work, we synthesized a series of di-alkynylated
Au8 clusters (2 - 4). In addition, we examined absorption properties in solid state and crystal
structures of the clusters to open new opportunities for solid-state material.
In a typical reaction, a methanol solution of 1∙(NO3)2 was treated with any one of alkynes in thepresence of sodium methoxide and the mixture was stirred for several days (Fig.1).
Di-alkynylations of Au8 clusters (2 - 4) after purification were confirmed by electrospray ionization(ESI) mass spectrometry. While broadening of absorptions of 2 - 4 in solid states was observed,
overall absorption profiles in liquid states were retained (Fig.2). Though alkynyl groups were
found to be situated at trans orientation on di-edge-bridged bi-tetrahedral Au8 structures of 2 - 4(Fig.1 top left), crystal structure of 2 only showed high symmetry (rhombohedral system) and ahoneycomb-like arrangement. Moreover, the unique crystal structure had large solvent
accessible void.

Figure 1. Syntheses of Au8 clusters (2 - 4).

Figure 2. Diffuse reflectance(solid lines) and absorption(dotted lines) spectra of 2 - 4.

References[1] K. P. Hall, D. M. P. Mingos, Prog. Inorg. Chem. 32 (1984) 237. [2] Y. Shichibu, K. Konishi,
Inorg. Chem. 52 (2013) 6570. [3] Y. Shichibu, Y. Kamei, K. Konishi, Chem. Commun. 48 (2012)7559. [4] Y. Kamei, Y. Shichibu, K. Konishi, Angew. Chem. Int. Ed. 50 (2011) 7442.
[5] N. Kobayashi, Y. Kamei, Y. Shichibu, K. Konishi, J. Am. Chem. Soc. 135 (2013) 16078.

B63

Structure and thermodynamics

Helium droplets doped with sulfur and C60
Martina Harnisch,1 Nikolaus Weinberger,1 Stephan Denifl,1 Paul Scheier,1 Olof Echt1,21Institut für Ionenphysik und Angewandte Physik, University of Innsbruck, Austria
2

Department of Physics, University of New Hampshire, USA

Sulfur is the element with the largest number of solid allotropes [1]. Sn molecules containing as
many as 10 atoms in various isomeric shapes have been identified in the vapor phase. The
ring-shaped S8 is the dominant species at low temperature but this is not apparent from cationicmass spectra because of strong electron-induced fragmentation.
Fig. 1 displays the relative yield of positively and negatively charged sulfur- and sulfur-C60 clusters
formed by electron ionization of doped helium droplets. In the absence of C60 the most abundantcations (Fig. 1a) have the stoichiometry (S8)m+ (integer m). Martin [2] has reported a similar pattern
but the preference for (S8)m+ ions was much less pronounced. The anion spectrum (Fig. 1b), on
the other hand, shows strong local minima in the yield for ions of the form (S8)mS-. These minima
reflect the virtual absence of atomic sulfur in the equilibrium vapor [1]. Conversely, the fact that
(S8)m- ions are not as prominent as (S8)m+ suggests thatcarbonmaterials

show

promise for energy related applications such as fuel cells,
batteries, and hydrogen storage [4]. Fig. 1c displays anegative-ion mass spectrum of helium droplets dopedwith sulfur and C60 (cationic C60-sulfur clusters have100 1000 10000

16

1000

microporous

Ion yield (arb. units)

those of neutral Sn which tend to form rings [3].

8
8

32

24

32

10

16

8

16

8

16

40

b) Sn24

8

40

24

32

32

24

32

24

32

40

40

c) C60Sn40

1found; ions of other stoichiometries occur at less than24

16

already been investigated by Martin and coworkers [5]).
A strong preference for ions of the form C60(S8)m- is

16

100

the chain-like structures of Sn- anions differ strongly from

Sulfur-dopeda) Sn+

10

electron attachment results in dissociation, too. Indeed,

contain two or more C60 molecules.

0.1

10 %. Similar distributions are obtained for anions that
040

Number of sulfur atoms n

References[1] R. Steudel (ed.), Topics in Current Chemistry vol. 230 (Springer, 2003).
[2] T. P. Martin, J. Chem. Phys. 81 (1984) 4426.
[3] M. D. Chen, M. L. Liu, L. S. Zheng, Q. E. Zhang, C. T. Au, Chem. Phys. Lett. 350 (2001) 119.
[4] G. M. Zhou, L. C. Yin, D. W. Wang, L. Li, S. F. Pei, I. R. Gentle, F. Li, and H. M. Cheng, ACS
Nano 7 (2013) 5367.
[5] F. Tast, N.Malinowski, M. Heinebrodt, I.M.L.Billas, T.P.Martin, J.Chem.Phys. 106 (1997) 9372.

B64

Reactivity and catalysis

Size- and Isomer-Dependent Reactivity of Nickel Oxide Cluster Ions
Studied by Ion Mobility Mass Spectrometry
Keijiro Ohshimo, Shohei Azuma, Tatsuya Komukai, Ryoichi Moriyama, and Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki,
Aoba-ku, Sendai 980-8578, Japan
Nickel oxide compounds are widely used as catalysts of valuable reactions such as oxidation ofcarbon monoxide (CO) [1]. It was recently reported that CO adsorption reactivity on nickel oxide
cluster ions is dependent sensitively on the cluster size, for example, the adsorption hardly occurs
on Ni7O6+ [2]. In this study, we have investigated the structures and reactivities of nickel oxide
cluster ions by ion mobility mass spectrometry (IM-MS).
Nickel oxide cluster ions were injected into an ion-drift cell by a pulsed electric field at a given time(t = t0). The cell was filled with He buffer gas with a pressure of 0.80 Torr. After running throughthe cell, the ions were injected into a time-of-flight mass spectrometer by another pulsed electricfields at a given time later from the first pulse, t = t0 + t (t : arrival time). We have obtained acollision cross section of an ion from its arrival time
distribution (ATD), using kinetic theory of ion transport.
We have also observed reactions between the cluster
ions with CO by adding 0.5-5 % CO gas to He in thecell.
Figure 1 shows the ATDs of NinOn-1+ (n = 5-9) cluster
ions. Observed bands of ATDs gradually shifted tolonger arrival time with increasing cluster size. For
Ni6O5+ and Ni7O6+, two Gaussian functions werenecessary for the fittings of the ATDs. Thus there areat least two isomers with different collision crosssections for Ni6O5+ and Ni7O6+ in the present
experimental condition.

By comparison with ourprevious IM-MS studies of transition metal oxide
clusters [3], these two isomers are assignable totwo-dimensional and three-dimensional structures.
We will also discuss the rate constants of CO
adsorption and subsequent reactions on nickel oxide
cluster ions.
Reference(s)[1] P. Konova et al. Chem. Eng. J. 122 (2006) 41.
[2] F. Mafuné et al. J. Phys. Chem. A 117 (2013) 3260.
[3] F. Misaizu et al., Chem. Phys. Lett. 588 (2013) 63;
J. Phys. Chem. A, in press.

Figure 1. Arrival time distributions of
NinOn-1+ cluster ions for n = 5-9.
Open circles are the observed ion
intensities, and the Gaussian curves
show components of isomers.

B65

Reactivity and catalysis

Protected but Accessible: Oxygen Activation by
Calixarene-stabilized Undecagold Cluster
Xi Chen,1 Hannu Häkkinen1,2,
1

Department of Chemistry, University of Jyväskylä, Jyväskylä, Finland2

Department of Physics, University of Jyväskylä, Jyväskylä, FinlandThis work was motivated by a recent experiment [1] and presents computational evidence of anovel way to stabilize gold nanoclusters with porous ligand layer facilitating access of small
reactant molecules to active metal sites [2]. We have validated that calixarenes can form aprotective but porous ligand layer on the surface of a sub-nanometer Au11 cluster, while
maintaining accessibility to metal sites of the core. Three out of 11 Au atoms (27%) remain
accessible to small reactant molecules, and it was shown here that binding and activation of up to
three dioxygen molecules per cluster can take place. In fact the calixarene-stabilized Au11 cluster
discussed here works in a similar way as part of an enzyme protecting the active reaction centerfrom reaction inhibitors but allowing for small molecules to access the reactive metal sites. Our
computational results provide strong support for the experiment and predict that this class of
stable hybrid metal-organic nanomaterial should be very interesting for catalyzing aerobic
oxidations at ambient conditions.

Figure 1:

The structure of Au11L5(O2 )3Reference(s)[1] de Silva, N.; Ha, J.-M.; Solovyov, A; Nigra, M. M; Ogino, I.; Yeh, S. W.; Durkin K. A.; Katz, A. Nature Chem.
2010, 2, 1062.
[2] Chen, X.; Häkkinen, H.

J. Am. Chem. Soc. 2013, 135, 12944.

Reactivity and catalysis

B66

The origin of the high selectivity and catalytic activity of small ruthenium
clusters in the methanation of CO
Sandra M. Lang,1 Thorsten M. Bernhardt,2 Marjan Krstić,2 and Vlasta Bonačić-Koutecký2,3
1
2

Institute of Surface Chemistry and Catalysis, University of Ulm, Germany

Interdisciplinary Center for Advanced Science and Technology, University of Split, Croatia
3

Department of Chemistry, Humboldt-University Berlin, Germany

The low temperature polymer electrolyte fuel cell (PEFC) has gained increasing importance for thegeneration of electrical energy in transportation and decentralized small scale appliances.
However, the typically employed hydrogen feed gas usually contains small amounts of CO which
can lead to poisoning of the catalyst in the PEFC. One promising approach for CO removal is thecatalytic reaction with hydrogen (methanation). At the same time the reaction of CO2 (also present
in the feed gas) with H2 should be avoided to prevent excessive hydrogen loss. For such selective
CO methanation very small (< 1 nm) zeolite supported ruthenium particle catalysts have beenshown to be very promising materials [1]. However, the origin of the activity and particular
selectivity of sub-nanometer ruthenium particles for fuel cell feed gas purification remains an open
question.
Toward this goal we employed gas phase ruthenium clusters Run+ (n = 2 – 6) as model systems
and investigated their reactive properties toward molecules contained in typical fuel cell feedgases in an ion trap experiment and via first-principles density functional theory calculations.
Three fundamental properties of these clusters are identified which determine the selectivity andcatalytic activity [2,3]: (i) high reactivity toward CO in contrast to inertness in the reaction with CO2;(ii) promotion of cooperatively enhanced H2 coadsorption and dissociation on pre-formed
ruthenium carbonyl clusters, i.e. no CO poisoning occurs; and (iii) the presence of low coordinatedRu-atom sites, which are particularly active for H2 coadsorption and activation. Furthermore, thetheoretical investigations provide mechanistic insight into the CO methanation reaction anddiscover a reaction route involving the formation of a formyl-type intermediate.
These insights from gas phase studies are for the first time directly compared to results obtained
from experimental studies on zeolite supported (sub-)nanometer size ruthenium particle catalysts
which have been performed in the group of R. J. Behm (Institute of surface chemistry and catalysis,
Ulm University). This comparison shows that free clusters cannot only serve as model systems formechanistic studies but can also open new routes for the rational design of catalytic materials
consisting of intrazeolite anchored small Ru clusters.
References[1] S. Eckle, M. Augustin, H.-G. Anfang, R. J. Behm, Catal. Today 181 (2012) 40[2] S. M. Lang, U. Förtig, T. M. Bernhardt, M. Krstić, V. Bonačić-Koutecký, J. Phys. Chem. A(2014) DOI: 10.1021/jp501242c[3] S. M. Lang, T. M. Bernhardt, M. Krstić, V. Bonačić-Koutecký, Angew. Chem. Int. Ed. 53 (2014)
5467

B67

Reactivity and catalysis

Low-temperature catalytic activity of CO oxidation driven by strong electronicinteraction between Pt-Ag bi-element cluster and Si surface
Hisato Yasumatsu1 and Nobuyuki Fukui2
1

Cluster Research Laboratory, Toyota Technological Institute,

2

In East Tokyo Laboratory, Genesis Research Institute, Inc., Chiba, Japan
We present experimental evidence that low-temperature catalytic activity is derived from strong
electronic interaction between a Pt cluster and a Si surface.

Temperature-programmed

desorption (TPD) measurements [1] in the thermal CO oxidation were repeated for a given cluster
sample, PtN or PtNAg1 (N=30, 60) [2]bonded to the (111) surface of a Si
substrate [3], with systematic change ofthe reactant amounts adsorbed asshown in Figure 1.

The peaks

observed in the TPD spectra were
deconvoluted

so

as

to

obtainprobabilities of individual reactions [4].
It was found that this system reveals
low-temperature reductive activation ofoxygen molecules, which is one of thecritical steps in the CO oxidation.
Furthermore, doping of only a single Ag
atom to the cluster as an electron donor
improves this activity.

Figure 1. TPD spectra of 13C16O18O produced in thermaloxidation of 13C16O by 18O2 catalyzed on Pt30 disks bonded
to a Si substrate at the various adsorption amounts of
13 16
C O at the constant 18O2 one of 8.5×10-11 cm-2.

These high performances are explained in terms of the efficient electron donation to O2 due tonegative charges accumulated at a sub-nano interface between the cluster disk and the silicon
substrate surface as a result of strong electronic interaction of them [5].

Namely, clusters

promoted by an appropriate environment are expected to become functional materials with ahigher performance than conventional bulk and nano materials. The results of this researchaccelerate approaches to the next step of mass synthesis of functional cluster materials.
References[1] H. Yasumatsu and N. Fukui, J. Phys. Conf. Ser. 438 (2013) 012004.
[2] H. Yasumatsu, Euro. Phys. J. D 63 (2011) 195.
[3] H. Yasumatsu, T. Hayakawa, S. Koizumi and T. Kondow, J. Chem. Phys. 123 (2005) 124709.
[4] H. Yasumatsu and N. Fukui, submitted to Phys. Chem. Chem. Phys. (2014).
[5] H. Yasumatsu, T. Hayakawa, S. Koizumi and T. Kondow, Chem. Phys. Lett. 487 (2010) 279.

Reactivity and catalysis

B68

Dynamics of truly monodisperse cluster catalysts under the STM
Y. Fukamori, F. Knoller, M. König, F. Esch, U. Heiz.
Chemie Department, Technische Universität München, Lichtenbergstr. 4, Garching, Germany
In our laboratory, we aim at uncovering the size-specific chemistry of supported clusters for theapplication in catalysis. By preparing supported clusters with the highest level of control possible,
in terms of deposition, substrate and clusters adsorption site, a local probe characterization ofisomer structures and single cluster reactivity can be realized, which will be further compared withintegral reactivity studies.
In this work, we present an STM ripening study of Pd clusters, produced by our size-selectedcluster source (laser ablation and quadrupole mass-selection). The size-selected clusters are
soft-landed on highly ordered epitaxial films of graphene and hexagonal boron nitride on Ru(0001)
and Rh(111). Moiré moieties formed on such films have been shown to be good candidates for thestabilization of clusters [1].
Our ripening studies show that on substrates with a low cluster-support interaction (e.g. Pd ongraphene/Rh(111)) the cluster ripen by a Smoluchowsky type mechanism, whereas on substrates
with a higher interaction (e.g. Pd on h-BN/(Rh(111)) Ostwald ripening is the predominantmechanism[2].
In order to get a more defined insight on the processes that lead to the ripening and to quantify thecluster-support interaction, an Atom Tracking device has been implemented and first results areshown.
References[1] B. Wang, B. Yoon, M. König, Y. Fukamori, F. Esch, U. Heiz, U. Landman, Nano Lett. 12 (2012)
5907-5912.
[2] Y. Fukamori, M. König, B. Yoon, B. Wang, F. Esch, U. Heiz, U. Landman, ChemCatChem 3(2013) 3330-3341.

B69

Reactivity and catalysis

Effects of Ir addition on gas-phase and supported Au nanoclusters towards
catalytic CO oxidation
Laura Michelle Jiménez-Díaz,1 and Luis Antonio Pérez1
1

Instituto de Física, Universidad Nacional Autónoma de México, Apdo. Postal 20-364, Mexico D.F.
01000, Mexico

Recent studies show that the addition of iridium to Au/TiO2 catalysts, stabilize them against
sintering and improves their catalytic activity for CO oxidation [1]. Furthermore, it has been foundthat Ir-Au/rutile catalysts have small iridium particles containing gold and having dimensions of theorder of 1 nm and, probably, these nanoparticles are responsible for the enhancement of theactivity of these catalysts for the CO oxidation [2]. In order to study this phenomenon, we
performed density functional calculations of the O2 adsorption on small bimetallic Au-Ir
nanoclusters, with sizes ranging from 4 to 6 atoms, both in gas-phase and supported on TiO2.
Moreover, we also comparatively studied the O2 dissociation in these systems by using thenudged elastic band method. The results suggest that the addition of Ir to Au clusters can enhancetheir catalytic activity towards CO oxidation.
This work was supported by PAPIIT-DGAPA-UNAM IN106714. Numerical calculations were
performed at Miztli supercomputer of DGTIC-UNAM (Project SC14-1-I-49).
References[1] A. Gómez-Cortés, G. Díaz, R. Zanella, H. Rodríguez, P. Santiago, J.M. Saniger, J. Phys. Chem.
C 113, 9719 (2009).
[2] X. Bokhimi, R. Zanella, C. Angeles-Chavez, J. Phys. Chem. C 114, 14101 (2010)

B70

Reactivity and catalysis

Theoretical investigation for isomerizaiton of allyl alcohol over Au cluster
Mitsutaka Okumura,1,2 Kohei Tada,1 Kohei Sakata,1 Hiroaki Koga,2 Takashi Kawakami,1 andShusuke Yamanaka1
1

Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama,
Toyonaka, Osaka 560-0043, Japan
2

Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30
Goryoohara, Kyoto 615-8245, Japan

Transformation of allylic alcohols to saturated carbonyl compounds is one of the interesting
reactions for chemical processes. This reaction basically contains a two-step sequential oxidation
and reduction. Isomerization of allylic alcohols enables one-step transformation, thus various
homogeneous catalysts have been developed over Ru and Rh containing catalysts.
On the other hand, since Haruta et al. invented that gold nanoparticles supported on metal oxides
remarkably high catalytic activity for CO oxidation at low temperatures, Au catalysts have attracted
growing interest not only in gas phase but also in liquid phase, particularly for the aerobic oxidationof alcohols. Lately, dehydrogenation of alcohol to aldehyde has been achieved even in theabsence of O2. One-pot reactions using hydrogen-borrowing strategy over Au catalysts, in whichhydrogen atoms produced by the first step alcohol dehydrogenation are used for the second step
reduction, has also emerged. Tokunaga have attempted this strategy to apply for the Au-catalyzed
isomerization of allyl alcohol to propanal.
In order to discuss this isomerization of allyl alcohol over Au catalysts, theoretical study was
performed using Au6 cluster, since Au6 cluster is the smallest cluster that has vertex and edge
atoms. From these calculations, it was found that the hydrogen transfer easily proceed on Auclusters and the first dehydrogenation step was the rate deterring step. Additionally, theprotonation to the enolate C–C double bond was also suggested by DFT calculations.
Reference[1] Tamao Ishida, Jun Aimoto, Akiyuki Hamasaki, Hironori Ohashi, Tetsuo Honma, Takushi
Yokoyama, Kohei Sakata, Mitsutaka Okumura, and Makoto Tokunaga, Chem. Lett. in press.

B71

Reactivity and catalysis

Synthesis of Ag@Pd/TiO2 catalysts in an aqueous solution for the hydrogengeneration from decomposition of formic acid at room temperature
Daisuke Shimamoto,1 Masashi Hattori,2 Takeshi Daio,3 and Masaharu Tsuji1,21

Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Japan2

Department of Applied Science for Electronics and Materials, Kyushu University, Kasuga, Japan

3

International Research Center for Hydrogen Energy, Kyushu University, Fukuoka, Japan

Formic acid (HCOOH) has received a great attention as an in situ source of hydrogen for fuel cells,
because it offers high energy density, is non-toxic and can be safely handled in aqueous solution.
Although there has been a lack of solid catalysts that are sufficiently active and/or selective forhydrogen production from formic acid at room temperature, Tedsree et al.1 reported that Ag
nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H 2
from formic acid at ambient temperature. We have recently studied preparation of Ag-Pd bimetallic
nanoparticles supported on TiO2 nanoparticles under two-step microwave heating in ethylene
glycol (EG) with a boiling point of 180 oC.2 Results show that catalytic activity of Ag-Pd particles isenhanced by about 300% in the presence of TiO2 support. It is reported that catalytic activity
Ag@Pd core-shell particles is higher than Ag-Pd alloy particles.1 Therefore, preparation of Ag@Pd
particles with low Ag-Pd alloy components is required for the formation of more active Ag-Pd
catalytic system.
In this study, Ag-Pd bimetallic nanocatalysts supported on anatase-type of TiO2 nanoparticles
have been prepared in an aqueous solution under microwave heating at 100 oC. At first,
anatase-type of TiO2 nanoparticles with average diameter of 10±2 nm were prepared as a catalytic
supportbyhydrolysis

1,5-pentanediol

under

of

titaniummicrowave

tetraisopropoxide(MW)heating.

in

Then

TiO2-supported Ag-Pd bimetallic nanocatalysts were preparedfrom formic acid using a two-step MW-polyol method forhydrogen production. In the first step, small Ag nanoparticles
were prepared under low-power MW heating (150 W). Then inthesecondstep,

monodispered

TiO2-supported

Ag-Pd

bimetallic particles were prepared under higher power MW
heating (150 W) for 20 min (Fig. 1). The hydrogen product rateof Ag@Pd/TiO2 from formic acid at 30 °C was measured to be
28.24 L / h g, which was higher than that of AgPd@Pd/TiO2

Fig.

1.

TEM

particles prepared in EG (16.00 L / h g). The higher catalytic

Ag@Pd/TiO2

activity can be explained by suppression of alloying in Ag-Pd

preparedparticles (Ag96Pd4 based on XRD data.)

heating.

by

image

of

catalysts
microwave

References[1] K. Tedsree, T. Li, S. Jones, C. W. A. Chan et al., Nat. Nanotech., 6 (2011) 302.
[2] M. Hattori, H. Einaga, T. Daio, and M. Tsuji, Nat. Commun., submitted for publication.

Reactivity and catalysis

B72

Reaction of aluminum cluster cations with a mixture of O2 and H2O gases:
Formation of hydrated-alumina clusters
Masashi Arakawa, Kei Kohara, and Akira Terasaki
Department of Chemistry, Kyushu University, Fukuoka, Japan
Aluminum is known as a reactive metal as we can imagine from the fact that it is readily oxidized
by O2 and/or H2O in the air to form a passive surface. Reduction of H2O by aluminum, forexample, is one of the efficient ways to produce H2. It is anticipated also that aluminum hydrides
are used as hydrogen storage materials. In this regard, clusters are attracting much attention formodeling interactions of metal surfaces with reactants. We have reported that aluminum-cluster
cations (AlN+) react with a H2O molecule to form AlNO+, which implies H2 generation [1]. In thepresent study, we investigated reaction of AlN+ toward a mixture of O2 and H2O gases to model
reactions in natural environments.
In the experiment, AlN+ (N = 1–14) were generated by a magnetron-sputter cluster-ion source.
They were mass-selected and guided into a reaction cell filled with a buffer He gas containing H2O
and O2.

The ions produced by the reaction of AlN+ with H2O and O2 were identified by aquadrupole mass analyzer.
Reaction products with a mass of 157 and 175 amu were observed for all the sizes except N = 1.
Since only Al+ was found to be inert, we speculated that these products originate from Al2+, which
is produced by dissociation of AlN+ (N ≥ 3). By controlling the partial pressures of O2 and H2O,
reaction intermediates such as Al2O+, Al2O3+, Al2O4H3+, and Al2O5H5+ were observed, and theprominent products were assigned to be Al2O6H7+ and Al2O7H9+ for 157 and 175 amu, respectively.
The chemical composition of these products, Al2O3(H2O)nH+, is similar to that of hydrated alumina
such as boehmite, diaspora, and gibbsite except for the proton. To obtain structural informationof these products, we performed collision-induced dissociation experiment of Al2O7H9+ (175 amu)
with an Ar gas, where products of 157, 139 and 121 amu were observed.

The prominent

products of 157 and 175 amu were thus identified as Al2O4H3(H2O)2+ and Al2O4H3(H2O)3+ with two
and three H2O molecules remaining intact, respectively.
We further investigated formation process of these protonated hydrated-alumina clusters byobserving the reaction steps to model reactions of aluminum in natural environments; eachreaction intermediate was generated in the cluster source, and reaction with either H2O or O2 was
examined in a step-by-step manner. It was found that reaction of aluminum with O2 and H2O toform alumina, Al2O3, at initial steps is followed by successive hydroxylation and hydration
reactions.
Reference[1] M. Arakawa, K. Kohara, T. Ito, and A. Terasaki, Eur. Phys. J. D 67 (2013) 80.

Reactivity and catalysis

B73

Adsorption and catalytic activation of the molecular oxygenon the metal supported h-BN
Andrey Lyalin,1 Akira Nakayama,1,2 Kohei Uosaki,3 and Tetsuya Taketsugu1,2
1

Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto, Japan2
3

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Global Research Center for Environment and Energy based on Nanomaterials Science(GREEN), National Institute for Materials Science (NIMS), Tsukuba, Japan

Adsorption and catalytic activation of the molecular oxygen on the hexagonal boron nitride (h-BN)monolayer supported on Ni(111) and Cu(111) surfaces have been studied theoretically using
density functional theory with the gradient-corrected exchange–correlation functional of Wu andCohen (WC) [1]. It is demonstrated that inert h-BN monolayer can be functionalized by the metal
support and become active for O2 activation [1-3]. It is shown that O2 adsorbs on h-BN/Ni(111) andh-BN/Cu(111) systems in two configurations, corresponding to the superoxo-like and peroxo-likestates of oxygen. It is shown that the metal substrate influences the molecular adsorption andchemical reactions on the supported h-BN surface via the mixing between metal d and h-BN πbands. Such an effect can open a new way to tune adsorption characteristics of O2 and reactant
molecules on h-BN by the selection of metal substrate.

Figure 1. Optimized structure of the molecular oxygen physisorbed on a free h-BN monolayer (left)
and chemisorbed on the h-BN/Ni(111) surface in on top (middle) and bridge (right) configurations.
References[1] A. Lyalin, A. Nakayama, K. Uosaki, and T. Taketsugu, Top. Catal. 57 (2014) 1032.
[2] A. Lyalin, A. Nakayama, K. Uosaki, and T. Taketsugu, J. Phys. Chem. C 117 (2013) 21359.
[3] K. Uosaki, G. Elumalai, H. Noguchi, T. Masuda, A. Lyalin, A. Nakayama, and T. Taketsugu,
JACS 136 (2014) 6542.

B74

Reactivity and catalysis

Reductive Activation of CO2 by Cobalt Cluster Anions
Akimaro Yanagimachi,1 Kiichirou Koyasu,1,2 and Tatsuya Tsukuda1,2
1

Department of Chemistry, The University of Tokyo, Tokyo, Japan
2

ESICB, Kyoto University, Kyoto, Japan

Development of catalysts that can activate chemically inert carbon dioxide (CO2) is desired for its
use as a reusable carbon source to establish sustainable society. Conventionally, Lewis basecatalysts have been used to activate CO2 by nucleophilic interaction at the carbon site of CO2 andsubsequent electron transfer [1]. Metal clusters are promising candidates for alternative catalysts,
because of their unique unsaturated surface sites and quantized electronic structures. In this study,
reaction of cobalt cluster anions (Con–) and CO2 were studied experimentally and theoretically.
The apparatus used in the present study is composed of four parts: a laser ablation cluster source,a reaction cell, a Wiley–McLaren type time-of-flight mass spectrometer, and a magnetic bottle typephotoelectron spectrometer [2]. Briefly, Con– produced by the laser vaporization method wasallowed to react with CO2 under a high pressure of He and the anionic products were analyzed by
the TOF mass spectrometer. Photoelectron spectra of Con– and ConCO2– (n = 5–9) were mesured
using the 3rd harmonic of Nd:YAG laser (355 nm). Fig. 1a shows a typical mass spectrum of thecluster anions produced by the laser ablation of a Co rod. The mass peaks of Con– were observed.
After the reaction (Fig. 1b), the peak intensities ofCon– decreased and the mass peaks assigned to
ConCO2– were newly observed via the following
reaction,
Con– + CO2 →ConCO2–.
Photoelectron band of Con– at low binding energy
region disappeared after the reaction with CO2.
The same trend was observed for all the clusters
studied here (n = 5–9). This suggests thatelectronic charge is transferred from Con– to CO2.
In order to confirm this interpretation, thegeometric and electronic structures of Co7CO2–
werestudiedbyDFT
calculationat–
B3LYP/LanL2DZ(Co), 6–311++G*(C, O) level. Fig.
Figure 1. Mass spectra of Con (a) beforeand (b) after the reaction with CO2.
2 shows the optimized structure. CO2 is bonded to
Co7– clusters through C and O. The bent structureof CO2 suggests that it is negatively charged.
Mulliken population analysis indicates the electrontransfer from Co7– to CO2. These experimental
and theoretical results indicate that CO2 can be
activated reductively by Con–.
References[1] T. Sakakura, J.-C. Choi, and H. Yasuda, Chem.
Rev. 107 (2007) 2365.
[2] T. Watanabe, T. Tsukuda, J. Phys. Chem. C
117 (2013) 6664.

–

Figure 2. Optimized structure of Co7CO2 .
The numbers in parenthesis indicate
Mulliken charge. Structure parameters of
free CO2 are also shown in brackets.

B75

Reactivity and catalysis

Theoretical study on the isomerization of small gold clusters induced by O2
adsorption
Min Gao,1 Daisuke Horita,1 Yuriko Ono,1 Andrey Lyalin,2 Satoshi Maeda1,2 and Tetsuya
Taketsugu1,2
1
2

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

Gold clusters possess unique catalytic activity in various oxidation reactions by molecular oxygen[1]. Several mechanisms have been proposed to investigate the origin of high catalytic activity ofgold clusters. No matter which route oxidation reactions follow, the adsorption and activation of O2
molecule on gold clusters are always the key initial step. There are two forms of oxygen adsorption
on gold clusters: the superoxo form (η1–AunO2) with only one O atom bounded to the gold cluster
and peroxo form (η2–AunO2) with O2 molecule bridging two gold atoms on the cluster surface.
Recently, Fielicke et al. observed these two adsorption forms for odd-sized gold clusters using
analysis of O-O vibrational stretching frequencies [2]. However, the origin of two vibrational
fundamentals for AunO2 is still not clear, because one or more isomers of the gold cluster as well
as more than one binding geometry of the oxygen molecule on gold cluster can coexist.
In the present work, we applied single-component artificial force induced reaction (SC-AFIR)
method [3] to search for the structural transformations upon adsorption of O2 molecule on goldclusters (Au3 – Au12). The stable geometrical structures, adsorption energies, vibrationalfrequencies, and charge transfers from gold clusters to oxygen molecule are investigated tounderstand the structure dependence on oxygen adsorption. It is demonstrated that oxygen
molecule adsorbs on the odd-sized gold clusters either in the peroxo or superoxo forms, but in thecase of even-sized gold clusters only peroxo form can exist. The O-O bond length in the η2–AunO2
form is longer than the one in η1–AunO2 form, which indicates that O2 is more activated in theη2–AunO2 form due to the more excess electron transfer from gold clusters. O2 molecule adsorbs
in the η1–AunO2 form on the most stable gold clusters, but in the η2-AunO2 form on theenergetically low-lying isomers. Oxygen molecule in the η2–AuO2 form is more active. Theinteraction energies between O2 and gold cluster in superoxo form are approximately twice aslarge as the binding energy in peroxo form. Although O2 molecule prefers to adsorb on the moststable structures in the form of η1–AunO2, it can be isomerized to η2–AunO2 with very low barrier.
The pathways of isomerization between gold clusters and AunO2 are also compared. More details
will be presented in poster session.
References[1] M. Haruta, T. Kobayashi, H. Sano, and N. Yamada, Chem. Lett. 16 (1987) 405.
[2] A. P. Woodman, G. Meijer, and A. Fielicke, J. Am. Chem. Soc. 135 (2013) 1727.
[3] S. Maeda, T. Taketsugu, and K. Morokuma, J. Comput. Chem. 35 (2014) 166.

B76

Reactivity and catalysis

Materials Development for Realization of Carbon-Neutral Energy Cycles
Miho Yamauchi,11International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University,
Fukuoka, Japan
2

JST-CREST, Saitama, JapanThe CO2 concentration of the atmosphere
has been inadvertently increased byconsuming finite energy resources of fossil
fuels, and increased concerns about climate
issues due to CO2 emissions have spurred
the development of alternative andsustainable energy cycle systems. We haveproposed novel energy cycles where
electrical power is generated by partial
oxidation of liquid fuels without CO2 emission,
resulting in CO2-free power generation, andfuels are regenerated by using renewableenergies, and fuels are regenerated from
Figure 1. Concept of carbon-neutral energy cycles.
oxidized wastes by using renewableenergies,1 i.e., carbon-neutral (CN) energy cycles.2 Among a number of energy carrying materials,
ethylene glycol (EG) can be cited as a fascinating candidate as it has a high boiling point(197.3 °C) and low vapor pressure (8 Pa at 20 °C). Previous studies have revealed that Pt-based
catalysts show the highest selectivity for partial oxidation of EG and mainly produce glycolic acid,i.e., 4-electron oxidation. For the sake of the efficient use of fuels and the suppression of CO 2
concentration in the environment, deeper oxidation of EG without CO2 emission should be the bestdesirable process. We herein demonstrate the successful synthesis of a well-mixed Fe-groupternary nanoalloy (NA) catalyst, a carbon supported FeCoNi NA catalyst (FeCoNi/C), that exhibits
selective EG electrooxidation to oxalic acid without CO2 emission in alkaline media, where the NA
structure were maintained throughout the catalytic reaction. Furthermore, an alkaline fuel cellfabricated with the FeCoNi/C anode catalyst and a solid oxide electrolyte was found to exhibit
power generation from EG without any precious-metal catalysts.3
References[1] M. Yamauchi, R. Abe, T. Tsukuda, K. Kato, M. Takata, J. Am. Chem. Soc., 133, 1150-1152(2011).
[2] M. Sadakiyo, H. Kasai, K. Kato, M. Takata, M. Yamauchi, J. Am. Chem. Soc., 136, 1702–1705(2014).
[3] T. Matsumoto, M. Sadakiyo, M. L. Ooi, S. Kitano, T. Yamamoto, S. Matsumura, K. Kato, T.
Takeguchi, M. Yamauchi, Scientific Reports, in press.

Reactivity and catalysis

B77

Adsorption and decomposition of NO
on foreign metal-doped copper cluster cations
Shinichi Hirabayashi1 and Masahiko Ichihashi2
1
2

East Tokyo Laboratory, Genesis Research Institute, Inc., Chiba, Japan

Cluster Research Laboratory, Toyota Technological Institute, Chiba, Japan

Doped metal and bimetallic clusters often exhibit different chemical properties from those of
single-component metal clusters. Here we demonstrate the results of the investigation ofadsorption and reactions of nitric oxide (NO) on foreign metal-doped copper cluster cations, CunX+(X = Al, Ti, and Rh), in the gas phase. The CunX+ clusters are produced by an ion sputtering
source, and their reactivity is measured by using a tandem-type mass spectrometer. The NO
adsorption cross sections for CunAl+ show an pronounced even-odd alternation in the region of n =8−16, where the clusters with odd-numbered n are more reactive than the adjacent ones with evenn. This alternation can be understood in terms of the electron pairing. In the reactions of CunTi+,
the reaction cross section tends to increase with increasing cluster size, and most of the doped
clusters exhibit significantly larger reaction cross sections than undoped Cu clusters [1]. The
results suggest that these doped clusters have relatively large NO adsorption energies. However,
the reactivity decreases rapidly above n = 11, and then Cu15Ti+ is totally unreactive toward NO,
which can be explained by its stability related to the electronic shell closing [2]. The
multiple-collision reactions are also investigated for some reactive clusters, CunAl+ (n = 9 and 11)
and CunTi+ (n = 7, 9, 11, and 12). These reactions result in the production of the cluster dioxides,
which is accompanied by the release of Cu atoms and an N2 molecule. This observation indicatesthat the decomposition of NO can proceed via dissociative adsorption on these clusters. Since it isconsidered that the process of dissociative adsorption involves more than one constituent atom,
Cu atoms should act as an active site with the foreign atom. On the other hand, for CunRh+, theNO adsorption cross sections are mostly smaller than those for reactive CunAl+ and CunTi+
clusters, and no clear evidence of NO decomposition is found.
Reference(s)[1] S. Hirabayashi and M. Ichihashi, J. Phys. Chem. A 118 (2014) 1761.
[2] E. Janssens, S. Neukermans, and P. Lievens, Curr. Opin. Solid State Mater. Sci. 8 (2004)
185.

B78

Reactivity and catalysis

withdraw

B79

Reactivity and catalysis

Base catalysis of [Nb6O19]8– and [Nb10O28]6–
Shun Hayashi,1 Seiji Yamazoe,1, 2 Kiichirou Koyasu,1, 2 and Tatsuya Tsukuda1, 2
1
2

Department of Chemistry, The University of Tokyo, Tokyo, Japan

Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto, Japan

Anionic metal-oxide clusters called polyoxometalates (POMs) with well-defined structures showpromise for a variety of applications including catalysts, electronic devices and chromic devices.
Recently, it was reported that polyoxotungstate acted as base catalysts for Knoevenagel
condensation reactions [1]. It is expected that polyoxoniobates (e.g. [Nb6O19]8– and [Nb10O28]6–)
show higher basicity than polyoxotungstates (e.g. [W6O19]2–) because niobium (group V) forms
more negatively charged POMs than tungsten (group VI). According to this hypothesis, we studied
basic nature of [Nb6O19]8– and [Nb10O28]6– theoretically and applied them as catalysts for
Knoevenagel condensation and CO2 fixation reactions for the first time.
DFT

calculations
8–[Nb6O19]

were

conductedfor6–and [Nb10O28] . Natural Bond Orbital

analysis indicated that the maximum negative
chargesofsurfaceoxygenpolyoxoniobates (–0.90 for [Nb6O19]

atoms
8–

in

and –0.86

6–for [Nb10O28] ) were larger than those inpolyoxotungstates (e.g. –0.72 for [W 6O19]2–).
This

resultsuggests

that

Figure 1: [Nb6O19]

8–(left) and [Nb10O28]

6–(right).

polyoxoniobates

possess more basic sites.
Na7H[Nb6O19]·15H2O and (TBA)6[Nb10O28] (TBA:
tetrabutylammonium)

were

synthesizedaccording to the methods reported in refs [2, 3].
Then, they were applied to Knoevenagel
condensation, a model reaction to evaluate basestrengths of catalysts. Na7H[Nb6O19]·15H2O
catalyzed condensation of ethyl cyanoacetate(pKa = 13.1) in heterogeneous system, whereas(TBA)6[Nb10O28] showed catalytic activity forcondensation of 4-methoxybenzyl cyanide (pKa
= 23.8) in homogeneous system (Figure 2). We
also found that (TBA)6[Nb10O28] acted as
catalysts for fixation of CO2 (0.1 MPa) with

Figure 2: Knoevenagel condensation catalyzed by
TBA6[Nb10O28] for nitriles with various pKa values(reaction temperature: (a) 30ºC, (b) 80ºC).

epoxide.
Reference(s)[1] N. Mizuno et al., Chem. Commun. 48 (2012) 8422. [2] S. Yamazoe et al., Chem. Lett. 42 (2013)
380. [3] A. Yagasaki et al., Polyhedron 29 (2010) 2196.

B80

Reactivity and catalysis

FT-ICR study of chemical reaction of acetonitrile molecules on cobalt clusters
Kazuki Ogasawara,1 Yuta Tobari,2 Yoshinori Sato,1 Makoto Saito,1 Shohei Chiashi,1
Toshiki Sugai,2 and Shigeo Maruyama1
1

Department of Mechanical Engineering, The University of Tokyo, Tokyo, Japan2

Department of Chemistry, Toho University, Funabashi, Japan

Intensity (arb. unit)

The chemical vapor deposition (CVD) method is the most common technique for production of
single walled carbon nanotubes (SWNTs). During the CVD process, an SWNT grows fromdecomposed carbon atoms on a catalytic metal particle fed by molecules such as CO, CH4 or
ethanol at high temperature. Therefore, understanding surface chemical reaction is criticallyimportant, however, little is known due to the complexity of these nanoparticles. Recently,
Thurakitseree et al. [1] reported that changing the carbon feedstock from pure ethanol to a few %mixture of acetonitrile (CH3CN) in ethanol during CVD drastically reduces the average diameter of
the SWNTs, and this change is reversible and repeatable. It is suggested that the nitrogen atoms
in acetonitrile molecules impeded the formation of larger diameter SWNT on the surface of
catalytic particles. However, the detailed mechanism of the reaction is also still not clear.
In this study, the chemical reactions of cobalt cluster cation with acetonitrile was observed by
Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer with direct injection laser
vaporization cluster beam source [2]. Cobalt clusters were trapped within the FT-ICR cell,subsequently acetonitrile was introduced. Figure 1 shows the typical mass spectrum of thereaction products from Co11+ clusters. Dotted lines indicate the simple chemisorption of acetonitrile
such as +CH3CN or +(CH3CN)2. We can also observe the dehydrogenated chemisorption such as+(CCN)2 or +(CCN)2(HCCN). Figure 2 shows the schematic diagram of the Co11(CCN)2+ cluster.
The drastic cluster size dependence of these reaction such as the change of simple/dehydrogenate chemisorption ratio was
Number of Cobalt atoms
observed. The difference of reactivity
11
12
13
compared with the ethanol (C2H5OH),+(CCN) 2(HCCN)
nitrogen-free molecules, and the cluster+CH3CNsize dependence of these reactions will
+HCCN*+(CCN) 2
also be discussed.
Fig.1 Chemisorption on Co11+

*

*

*

C

C

C

N

0

50
100
Relative Mass (amu)clusters; ＊indicatesFig.2 Schematic diagram ofpeaks originated from Co12+ or Co13+.
Reference(s)[1] T. Thurakitseree, et al., ACS Nano, 7 (2013) 2205.
[2] S. Maruyama, et al., Rev. Sci. Instrum., 61 (1990) 3686.

Co11+

C

H2 desorptionN

Co11(CCN)2+ cluster.

B81

Reactivity and catalysis

Gold Nanoparticle-Catalyzed C–H Bond Functionalization for Biaryl Synthesis
Yoshiyuki Mise,1 Shohei Aikawa,1 Tamao Ishida,1,5 Ryota Akebi,1 Akiyuki Hamasaki,1 Hironori
Ohashi,2 Tetsuo Honma,3 Tetsuro Tsuji,4 Yasushi Yamamoto,4 Mitsuru Miyasaka,4 Takushi
Yokoyama,1 Makoto Tokunaga1
1Graduate School of Sciences, Kyushu University, Fukuoka, Japan
2

3

Faculty of Arts and Science, Kyushu University, Fukuoka, Japan

Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), Hyogo, Japan
4

5

UBE Industries Ltd., Yamaguchi, Japan

Research Center for Gold Chemistry, Tokyo Metropolitan University, Tokyo, Japan

Direct transformation of C–H bonds into C–C bonds for synthesizing biaryl compounds has been agreat issue in organic chemistry over the decade. Although many kinds of homogeneous metal
catalysts, including Ru, Pd, and Au complexes have been developed, heterogeneous metal
catalysts are still scarce. Very recently, Au nanoparticles (NPs) supported on TiO2 has beenreported to be catalytically active for C–H/C–H coupling of arenes into biaryls, but to control theregioselectivity of substrates remained challenge. In this work we studied on the C–H/C–H
coupling of dimethyl phthalate (DMP) to produce tetramethyl biphenyltetracarboxylate(S-DM/A-DM) over supported Au NPs, and found that Au catalysts can produce S-DM withexcellent regioselectivity. As shown in Table 1, Au catalysts showed higher catalytic activity thanPd catalysts. Among the catalysts tested, Au/Co3O4 and Au/ZrO2 exhibited the highest activity(entries 4 and 5). In addition, Au catalysts showed excellent regioselectivity to S-DM without theaddition of ligands. After optimization of reaction conditions for Au/ZrO2, the dimer yield increased
up
Table 1. Oxidative coupling of DMP.

a)

to

73%

excellent selectivity(entryEntry

Catalyst

1

with

6).

We

confirmedthathomogeneous

Au

complex,

Au(OAc)3

Conv. (%)

Dimer Yield (%)

S/(S+A) (%)

PdO/Co3O4

7

1

0

was inactive under2

Au/TiO2

45

27

85

our conditions (entry

3

Au/MnO2

39

20

95

7),

4

Au/Co3O4

49

48

94

without Au did not

5b)

Au/ZrO2

66

51

88

catalyze

6c)

Au/ZrO2

88

73

95

reaction (entry 8),

7

Au(OAc)3000suggesting

8

Co3O4

0

0

0

Au(0) NPs are thea) Conditions: DMP (1 mmol), catalyst (metal 4 mol%), AcOH (0.5 mL), O2 (1.5MPa), 150 °C, 18 h. b) O2 (1.8 MPa). c) O2 (1.8 MPa), 120 °C, 96 h.

andcatalyticallyspecies.

Co3O4
this
that
activeReactivity and catalysis

B82

Gas Phase Modeling of the Catalytically Active Centers in Iron Sulfur Proteins
Heiko Heim, Thorsten M. Bernhardt, Sandra M. Lang
1

Institute of Surface Chemistry and Catalysis, University of Ulm, Germany

Small iron-sulfur (FeS-)clusters are often considered as the active reaction centers of the mostcommon naturally occurring proteins (FeS-proteins) and are thus of fundamental importance for all
living organisms. Apart from their role as electron transfer medium in biochemical redox reactions,
FeS-clusters are especially important as biocatalysts in numerous pivotal processes [1]. In
particular, the mild reaction conditions and the ability of such biocatalysts to activate molecular
nitrogen renders them ideal materials for a "green", i.e. environmentally friendly and sustainable,
catalysis. Thus, the investigation of the catalytic mechanisms in enzyme reactions is not only ofparticular importance for a basic understanding of the functionalities of life; enzymes as
biocatalysts also represent ideal systems to learn from nature and to use this knowledge for thedevelopment of new catalytically active and selective materials.
Toward this goal we aim to mimic the active centers of FeS-proteins in form of gas phase clusters.
In a first step these clusters have been prepared in a CORDIS sputter source [2] by sputtering ofbinary targets pressed from iron and sulfur powder. However, iron and in particular iron powder
easily oxidizes at air which should lead to a considerable amount of oxygen in the target and thus
in the produced clusters. To unambiguously assign the mass peaks in the produced cluster
distribution and to gain insight into the degree of a possible oxygen contamination of the targets, aseries of different targets have been produced and the formation and stability of iron oxide andiron sulfur clusters has been investigated in detail
In a second step some FeS-cluster cations (FeS)n+ (n = 2, 4) have been mass-selected from theproduced cluster distribution and their reactivity towards N2, H2, and mixtures thereof have been
investigated in an ion trap experiment [3]. Temperature dependent product distributions inconjunction with kinetic data provide detailed insight into the reaction mechanism as well as theenergetics of the reaction between (FeS)n+ and N2 and H2, respectively, as well as a potential
ammonia synthesis reaction.

Reference(s)[1] H. Beinert, R. H. Holm, E. Münck, Science 277 (1997) 653[2] R. Keller, F. Nöhmeier, P. Spädtke, M. H. Schönenberg, Vacuum 34 (1984) 31[3] T. M. Bernhardt, Int. J. Mass Spectrom. 243 (2005) 1B83

Reactivity and catalysis

Thermal stability and reactivity with CO molecules of cerium oxideand gold-appended cerium oxide clusters
Toshiaki Nagata, Ken Miyajima, and Fumitaka Mafuné
Department of Basic Science, School of Arts and Sciences, The University of Tokyo, Tokyo, Japan
Cerium oxide (CeO2, ceria) is widely used for automotive three-way catalysts that convert harmful
exhaust gases including NOx, CO, and small hydrocarbons into N2, CO2, and H2O. Ceria is also
used as a support of catalysts; one of the most important supported materials is nanosized gold [1].
In this work, we studied thermal stability and reactivity with CO molecules of cerium oxide andgold-appended cerium oxide cationic clusters (AumCenO2n+x+; m = 0–2, n = 3–7, x = −1–+2) in thegas phase using a newly developed post-heating method [2].
The clusters were prepared by laser ablation of rod-shaped CeO2 and Au targets using focusedsecond harmonic of Nd:YAG pulse laser in the presence of oxygen diluted in helium. The
generated clusters were introduced into a reaction gas cell filled with CO diluted in helium,
followed by passing in a temperature controlled heating tube (post-heating). Then the clusters
were introduced into a vacuum and detected by a time-of-flight mass spectrometer.
Figure 1 shows the abundance distributions of generated AumCenO2n+x+ clusters at room
temperature and after heating up to 573 K. Figure 2 shows the cluster ion intensities as functionsof temperature in the heating tube. In a high temperature, oxygen-excess clusters released O2
molecules and turned to be compositions of CenO2n+x+ (x = −1, 0) and AumCenO2n+x+ (m = 1, 2; x =0, +1), which are considered to be the stable stoichiometry. The activation energies (Ea) of O2
releasing were estimated from the temperature dependence based on Arrhenius equation.
We observed CO oxidation and CO adsorption reactions on cerium oxide clusters, although only
CO adsorption was observed on gold-appended cerium oxide clusters. There is significant size
dependence in reactivity with CO. The CO attached clusters released CO molecules by the
post-heating. The Ea of CO releasing processes were estimated in the same way as O2 releasing.
m=0

m=1

m=2

2
1
x 0
−1
−2
3 4 5 6 7(b) 573 K
m=0

3 4 5 6 7

3 4 5 6 7

m=1

m=2

2
1
x 0
−1
−2

min
3 4 5 6 7

3 4 5 6 7(a)1.0Relative
Intensity
Relative Intensitymax

Ce3O8+→Ce3O6++O2 Ea=0.34 eV
Ce3O7+→Ce3O5++O2 Ea=0.55 eV
0.8+

0.6 Ce3O7

Ce3O6+

0.4

0.2

Ce3O8+

0.0300

3 4 5 6 7

Number of Ce atoms (n)Figure 1. Intensities of AumCenO2n+x+
at (a) r.t. and (b) 573 K.

Ce3O5+

400
500
Temperature (K)Temperature(K)(b)0.8Relative
Intensity
Relative Intensity(a) 299 K

600

0.6

Au2Ce3O8+ → Au2Ce3O6+ + O2
Ea = 0.37 eV

Au2Ce3O7+

0.4

Au2Ce3O8+

Au2Ce3O6+

0.2

0.0
300

400

500

Temperature (K)Temperature(K)

Figure 2. Relative intensities of (a) Ce3O5–8+ and (b)Au2Ce3O6–8+ as functions of heating temperature.

References[1] M. Haruta, Catal. Today 36 (1997) 153.
[2] K. Morita, K. Sakuma, K. Miyajima, and F. Mafuné, J. Phys. Chem. A 117 (2013) 10145.

600

Reactivity and catalysis

B84

Enhancement of photocatalytic activity of TiO2 nanoparticles by addition of Ag
nanoparticles
Mari Yonemura, Naoki Nishida, Hideki Tanaka
Department of Applied Chemistry, Chuo University, Tokyo, JapanTiO2 nanoparticles have drawn much attentions because of their photocatalytic activity. However,the photocatalytic performance of traditional TiO2 nanoparticles is restricted due to lack ofabsorption for visible light. In this study, we examined to load Ag nanoparticles, which have strong
absorption of visible light, onto the TiO2 nanoparticles and measured the visible-light photoactivityof TiO2 nanoparticles by addition of Ag nanoparticles.
Ag nanoparticles were produced by gas aggregation method heated at 1100 oC with N2 gas flow at
2.0 slm, and were directly sprayed on TiO2 nanoparticles. The sample thus prepared was
immersed to azobenzene methanol solution, and were irradiated for 4 hours by visible light.
Supernatant of the obtained solution was analyzed by UV-vis spectroscopy.
Figure 1 shows the absorption spectrum for the sample before and after irradiation. The dominantpeak at ～316 nm was attributed to azobenzene. The absorption for this peak was drasticallydecreased for the after-irradiation sample. Since the azobenzene molecule is known to be stablefor visible-light irradiation, this decrease is considered to be caused by photocatalytic activity of thepresent sample. In addition, the degradation rate for the sample (39 %) was higher than that forthe pristine TiO2 nanoparticles (23 %) . This indicates that addition of Ag nanoparticles effectively
improve the photocatalytic activity of TiO2 nanoparticles.

Figure 1. The absorption spectrum for the sample before (red dashed line) and after (blacksolid line) visible light irradiation for 4 hours.

B85

Reactivity and catalysis

Towards the Creation of Functionalized Metal Nanoclusters and Highly Active
Photocatalytic Materials Using Thiolate-Protected Magic Gold Clusters
Yuichi Negishi
Department of Applied Chemistry, Faculty of Science and Photocatalysis International ResearchCenter, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 Japan.
Advances in developments in nanotechnology have encouraged the creation of highly
functionalized nanomaterials. Because of their nanoscale size (< 2 nm), thiolate-protected goldclusters (Aun(SR)m) exhibit size-specific physical and chemical properties not observed in bulk
metals. Therefore, they have attracted attention as functional units or building blocks in
nanotechnology. The highly stable, magic Aun(SR)m clusters possess great potential as new
nanomaterials. We are studying the following subjects related to magic Aun(SR)m clusters: (1)establishing methods to enhance their functionality, (2) developing high-resolution separation
methods and (3) utilizing the clusters as active sites in photocatalytic materials. Through thesestudies, we aim to create highly functional metal nanoclusters and apply them as highly active
photocatalytic materials. The results of our efforts to date are summarized in this presentation.

Figure 1. Our study towards the creation of functionalized metal nanoclusters and highly active
photocatalytic materials.

B86

Reactivity and catalysis

Formation and structural analysis of composite of Ag nanoplates with TiO2
nanoparticles
Hiroki Nanjyo, Ken Iwai, Naoya Kinoshita, Naoki Nishida, and Hideki Tanaka
Department of Applied Chemistry, Chuo University, Tokyo, JapanAg triangular nanoplates have attracted much attention owing to their unique geometric structure
and optical properties which indicate that they have the potential for use in various applications.
These unique points are known to be complementary to each other since their optical properties
are induced by surface plasmon resonances that originate from their structure. On the other hand,
TiO2 nanoparticles have been commercialized for the purposes of self-cleaning walls in houses,
toilets, interior walls in tunnels, etc. In principal, TiO2 nanoparticles have been much attention as
photocatalytic materials. In this study, we have demonstrated the composition of Ag nanoplateswith TiO2 nanoparticles that combines the best of both and investigate their structure.
Ag

triangular nanoplates

were synthesizedby photoreduction of AgNO3 with

PVP

(polyvinylpyrrolidon) [1]. The obtained nanoplates were mixed with TiO2 aqueous solution. The
structure of obtained sample was analyzed by scanning transmission electron microscope (STEM).
In addition, optical property of obtained solution was analyzed by optical spectroscopy.
The triangular nanoplates and spherical nanoparticles were observed by STEM image. The
average diameters of triangular nanoplates and spherical nanoparticles were ~ 100 nm and ~ 35
nm respectively. The spherical nanoparticles were expected TiO2 nanoparticles from these sizes.
On the other hand, triangular nanoplates were expected Ag triangular nanoplates from theseshapes. Furthermore, extinction spectrum of the obtained solution exhibited two peaks at ~ 350
nm and ~ 700 nm. The peak at ~ 350 nm is ascribed to the TiO2. This indicated that the obtained
sample were contained TiO2 nanoparticles. In addition, the peak at ~ 700 nm is characteristic
signal for Ag triangular nanoplates [1]. This indicated that the obtained sample were contained Ag
triangular nanoplates.

Reference[1] H. Murayama, N. Hashimoto and H. Tanaka, Chem. Phys. Lett 482 (2009) 291.

B87

Reactivity and catalysis

Instantaneous cooling of metal clusters by collision with rare gas clusters– Incorporation mechanism of a cobalt cluster ion into an argon cluster
1

Hideho Odaka, 2Masahiko Ichihashi

12

East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa, Japan
Cluster Research Laboratory, Toyota Technological Institute, Ichikawa, Japan

Cryogenic cooling has a huge advantage for spectroscopic measurements with high resolution,and therefore the structural difference of reacting molecules can be distinguished, which aredissociatively or molecularly adsorbed on metal clusters. Especially, instantaneous cooling has
been achieved by incorporation of these metal clusters into a helium cluster to suspend chemical
reactions at the beginning or an intermediate state. Thus far, a small metal cluster has been
formed in a helium cluster by sequential pick-up of metal atoms, the size of which has been clearly
identified by IR spectroscopy because of the advantage of few isomers. To simplify themeasured spectra, we developed a novel method that a size-selected metal cluster ion isincorporated into a rare gas cluster by merging two cluster beams. We formed cluster complexes
from cobalt cluster ions and argon clusters, and discuss the incorporation mechanism in thispresentation.
Cobalt cluster ions were produced by laser ablation and their translational energy spread was
reduced by the collision with helium buffer gas in a gas cell. The cluster ions, size-selected by aquadrupole mass selector (QMS), were deflected into an octupole ion guide for merging collision(IGcol) by a quadrupole ion bender. Neutral argon clusters were produced by supersonic
expansion from a pulse valve with the stagnation pressure of 20 bar and the pulse width of 250 s.
The argon cluster beam was overlapped and merged with the cobalt cluster ion beam in the IGcol
at a low relative velocity (Vrel). Formed cluster complexes were analyzed by another QMS.
Size distribution of complex ions, Co2+Arn, formed by the collision of Co2+ with ArN is shown in Fig.
1. The maximum number of argon atoms attached on Co2+ is expected to be more than 30.
The intensity of product ions decreases with n monotonically, but more gradually at Vrel = 0.6 km
s-1 than Vrel = 1.3 km s-1, and almost levels off above n ~ 25. Co2+Arn is considered to be formed
via the sequential evaporation of argon atoms from Co2+ArN for relaxation of excess internalenergy as follows;
Co2+ + ArN → Co2+ArN → Co2+Arn + (N – n) Ar. (1)The size distribution of reactant ArN is supposed to follow a
log-normal distribution [1], and then the size distributions of
product Co2+Arn calculated reproduce those experimentallyobtained very well as shown in Fig. 1. The relative
velocity of 0.6 km s-1 corresponds to the collision energy of
0.2 eV, and the average number of evaporated Ar atoms
from Co2+ArN is estimated to be three.
+Fig. 1.
Size distributions of Co2 Arn.
Intensities were normalized to unreacted+
Co2 . The broken lines are fitting curves.

Reference[1] J. Harms, J.P. Toennies, and F. Dalfovo, Phys. Rev. B 58 (1998) 3341.

Reactivity and catalysis

B88

Surface oxide luminescence of Silicon nanoclusters
Hanieh Yazdanfar1, Gediminas Galinis1, Mike J. McNally1, Mumin. M. Koç1, Oliver Youle1,
Gauthier Torricelli1, Mark Watkins1, Klaus von Haeften1.
1

Department of Physics and Astronomy, University of Leicester, UK

Fluorescent silicon nanoclusters are of considerable interest, both as means of studying thefundamental properties of silicon, the most important technological material of our age, but also for
their many possible applications. Luminescent clusters of silicon have applications in
optoelectronic devices [1] and lasers [2], as well as for biological labels [3] and sensors [4], it’s low
toxicity giving it an advantage over other light emitting materials.
Silicon nanocluster solutions have been produced by deposition of atomic silicon on a liquid jet invacuum. XPS analysis confirms that the silicon is present in a high oxidation state and that theclusters are extremely oxygen rich, and FTIR shows the presence of bonds linked to SiO, SiO2
and SiO3 [5,6]. Clusters show a solvent sensitive fluorescence band at 350 – 420 nm and solvent
transfer is fully reversible between ethanol and water. The solvent exchange suggests thatfluorescence originates from the solvent / cluster-surface interface. These observations and otherwork in the field suggests the fluorescence emerges from oxygen rich surface states [6].
Reference(s)[1] K. M. Noone, D. S. Ginger, ACS Nano, 3 (2009) 261 – 265[2] L. Canham, Nature, 408 (2000)[3] Y. He, Y. Su, X. Yang, Z. Kang, T. Xu, R. Zhang, C. Fan, S. Lee, J. Am. Chem. Soc, 131 (2009)4434-4438[4] G. Wang, S. Yau, K. Mantey, M. H. Nayfeh, Optics Communications, 281 (2008) 1765 – 1770
[5] B. Tremblay, P. Roy, L. Manceron, M. E. Alikhani, D. Roy, J. Chem. Phys, 104 (1996) 2773
[6] X. Yang, X. L. Wu, S. H. Li, H, Li, T. Qiu, Y.M. Yang, P. K. Chu and G. G. Siu, App. Phys. Lett.
86 (2005) 201906.

B89

Reactivity and catalysis

Autoionization in cluster Coulomb explosion studied bymagnetic time-of-flight ion imaging
C. Schaal, R. Irsig, S. Skruszewicz, J. Tiggesbäumker, and K.-H. Meiwes-Broer
Institut für Physik, Universität Rostock, Universitätsplatz 3, D-18051 Rostock, Germany
The Coulomb explosion of small argon clusters exposed to intense ultrashort optical laser pulses
is studied by energy-momentum spectroscopy.

A position sensitive multi-channel plate

delay-line detector is incorporated to record the temporal and spatial signals of all ionic species
entering the magnetic field region.

From the ion energies and momentums, charge state

selective kinetic energy distributions have been extracted. The rapidly expanding highly charged
ion cloud shows signatures of autoionization of Rydberg-like matter, see Fig. 1.

The

spectrometer extends our current instrumentation to study intense laser-cluster interactions and inprinciple allows for the analysis of cluster Coulomb explosions on a single shot basis.

Figure 1: Magnetic deflection time-of-flight imaging spectrum of the Coulomb
explosion of argon clusters (N=1000) exposed to intense femtosecond laser
pulses (L = 110 fs, IL = 2.3×1015 W/cm−2, double pulse delay t = 500 fs).

AUTHOR INDEX

Abe, Yurika: B34
Achiba, Yohji: B29, B30, B34
Acuña-galván, Israel: A54
Adnan, Rohul: HT12
Adolph, Marcus: INV17, HT19, A5
Aguado, Andrés: A22
Aikawa, Shohei: B81
Aikens, Christine M.: INV12
Aimoto, Jun: A84
Akagi, Hiroshi: A6
Akebi, Ryota: B81
Akimoto, Yusuke: B44
Al Qahtani, Hassan: HT12
Albrecht, Wiebke: HT14
Al-hada, Mohamed: HT16
Alonso, Julio A: HT20
Alvino, Jason: HT12
Anderson, David P.: HT12
Anderson, Scott: INV9Andersson, Mats: B4
Andersson, Gunther: HT12
Andersson, Tomas: HT2, A13
Ando, Kota: A16, A53
Antoine, Rodolphe: INV8
Anton, Josef: A24
Aoki, Takuya: A87
Arakawa, Masashi: A16, A17, A53, A65, B72
Arii, Setsuka: B59
Asakura, Kiyotaka: A51
Asmis, Knut R.: HT5, A69
Azuma, Shohei: B64
Azuma, Toshiyuki: A43
Bakker, Joost M.: HT17, A9
Bals, Sara: B11
Bandelow, Steffi: HT24, B37
Bando, Kyoko: A77
Barke, Ingo: INV17
Barrabes, Noelia: A49, A73
Bartling, Stephan: INV17
Barzebar, Hamid Reza: B31
Baxter, Eric: INV9
Bellacicca, Andrea: INV14
Beltran Sanchez, Marcela: A19
Beltran, Marcela R.: A18
Beniya, Atsushi: A70

Bennett, Trystan: HT12
Bernhardt, Sandra M.: B66
Bernhardt, Thorsten M.: INV19, A32, A33, B82
Bischoff, Florian A.: A69
Bisht, Manisha: B8
Björneholm, Olle: HT2, A13
Boesl, Ulrich: A71
Böhme, Diethard K.: INV5, A45
Bonačić-koutecký, Vlasta: B66
Borghi, Francesca: INV14
Bostedt, Christoph: HT19, A4, A5
Bowlan, John: HT7, B2
Brown, Simon A.: INV15, B8, B11
Buendia Zamudio, Fernando: A18, A19
Bürgi, Thomas: A7, A49, A73
Cabria, Iván: HT20
Calvo, Florent: B49
Cao, Lu: A74
Chen, Xi: B65
Chen, Hsin-Yi Tiffany: B6Chen, Xuejiao: A38
Chen, Zhongfang: B50
Cheng, Daojian: A66
Chernyy, Valeriy: A9, B26
Chiashi, Shohei: B80, A82
Chipman, Daniel: B27
Chittari, Bheema Lingam: HT1, A50, A72
Colombo, Luciano: INV14
Couet, Sebastien: INV15, B8
Coutino-gonzalez, Eduardo: B24
Daio, Takeshi: A47, B71
Daxner, Matthias: INV5
De Heer, Walt: B2
De Wijs, Gilles: B52
Delin, Anna: A21, B2
Denifl, Stephan: INV5, A45, B63
Di Marco, Igor: A21, B2
Di Vece, Marcel: HT14, B14
Dieleman, Dennis: B26
Ding, Feng: HT10
Dolamic, Igor: A7
Duft, Denis: INV6
Düsterer, Stefan: A5
Eberhardt, Wolfgang: HT16
Echt, Olof: INV5, B63

Egashira, Kazuhiro: A16
Eguchi, Daichi: B55, B58
Eguchi, Toyoaki: A23, B38
Eilers, Joren: B14
Endo, Hitomi: B34
Eriksson, Olle: A21, B2
Eritt, Markus: INV6
Esch, Friedrich: B68
Fagiani, Matias R.: HT5, A69
Fennel, Thomas: INV17
Ferguson, Kenneth R.: A4
Fielicke, André: HT7
Flückiger, Leonie: INV17, HT19, A5
Fostner, S.: INV15
Fournier, Joseph: HT25
Fron, Eduard: B24
Fujii, Masanori: A39
Fujima, Nobuhisa: B54
Fukamori, Yves: B68
Fukuda, Naoaki: A62
Fukuhara, Mikio: B54
Fukui, Nobuyuki: A32, A56, B67
Fukuoka, Hiroshi: A62
Fukuzawa, Hironobu: A4, A15
Furukawa, Takeshi: A43
Futamata, Masayuki: A11, A12, A77
Gaffga, Maximilian: HT25
Galinis, Gediminas: A3, B39, B88
Gao, Junfeng: HT10
Gao, Min: A78, B75,
Garzón, Ignacio L.: HT6, A54
Gaston, Nicola: HT3
Gazoni, R.: INV15
Ge, Gui-xian: B32
Gell, Lars: B17
Gewinner, Sandy: A69
Ghisleri, Cristian: INV14
Ghosh, Saurabh: A21, B2
Giordano, Livia: B6
Golovko, Vladimir: HT12
Gorkhover, Tais: HT19, A5
Götz, Daniel A.: A2, B43
Grandjean, Didier: B24
Greisch, Jean-Francois: INV16
Grigg, J.: INV15

Hakkinen, Hannu: INV11, A8, A10, A37, B17,
B45, B65
Halder, Avik: HT4
Hamada, Toshiyuki: A40
Hamasaki, Akiyuki: A84, B81
Hamasaki, Yuki: B21
Hampe, Oliver: INV16
Han, Junhao: B40
Han, Min: A38, A62
Handa, Saori: A11
Hansen, Klavs: A43, A44
Harabuchi, Yu: A55
Harding, Dan: HT7
Harnisch, Martina: B63
Hartmann, Hannes: INV17
Hatakeyama, Yoshikiyo: A42, A51, B28, B48
Hatsui, T.: A4
Hattori, Masashi: A47, B47, B71
Hayakawa, Tetsuichiro: A16
Hayashi, Shun: B79
Hayashita, H.: A15
Heim, Heiko: B82
Heiz, Ulrich: A71, B68
Henschel, Henning: B15
Hevia, Miguel A.G.: A73
Hewer, Joachim: HT25
Hidaka, Hiroshi: A61, B61
Higashi, Yuuma: B19
Higo, Tohru: B13
Hillion, Arnaud: B11
Hirabayashi, Shinichi: A68, B77
Hirata, Hirohito: A70
Hirata, Naoyuki: A23
Hirose, Saki: B48
Hirsch, Konstantin: HT22, B9, B10
Hofkens, Johan: B24
Höltzl, Tibor: A34
Honma, Tetsuo: A84, B81
Horita, Daisuke: B75
Horiuchi, Shin: A77
Hoshino, Toshiharu: B54
Houben, Kelly: B8, B11
Hu, Michael Y.: B8Huang, Xiaoming: HT21, B50, B51
Huang, Xin: B20

Hutchison, Christopher: A4
Iancu, Violetta: B6
Ichihashi, Masahiko: A68, B77, B87
Iguchi, Naoyuki: B28
Iino, Ryota: INV13
Imamura, Kentaro: B13
Inouye, Yasushi: B20
Irsig, R.: B89
Ishibashi, Chiaki: B41
Ishida, Takuya: B25
Ishida, Tamao: A84, B81
Ishikawa, Yoshie: B19
Ishikura, Maho: A12
Ishitobi, Hidekazu: B20
Isomura, Noritake: A70
Isono, Hideo: A67
Itakura, Ryuji: A6
Ito, Gen: A43
Ito, Nobuaki: B30
Ito, Shota: A42
Ito, Tomonori: A16, A17
Ito, Y.: A4Ito, Yosuke: B30
Itoh, Akio: B60
Iwai, Ken: B86
Iwasa, Takeshi: A20, B38
Iwata, Suehiro: B41
Jacob, Timo: A24
Jäger, Patrick: INV16
Jalink, Jeroen: HT17
Janssens, Ewald: INV18, A44, B6, B11
Jiang, Cheng-huan: B32
Jiménez-díaz, Laura Michelle: B69
Jin, Rongchao: INV3
Jinnouchi, Ryota: B35
Jochmann, Kira: A33
Jochum, Johanna: B8
Johansson, Christer: B4
Johnson, Mark: HT25
Johnston, Roy L.: A2, B43
Joti, Y.: A4
Judai, Ken: A42, A46, A51, B28, B48
Kaiser, Alexander: INV5, A45
Kajiya, Shuji: B44
Kakeshita, Tomoyuki: B3

Kamali, Saeed: B4
Kameshima, T.: A4
Kanatani, Yayoi: B13
Kanazawa, Naoki: B29
Kane, Matthew: INV9
Kappes, Manfred: INV16
Katsnelson, Mikhail I.: A21, B2, B52
Kawakami, Takashi: B70
Kawashima, Minami: A67
Kaydashev, Vladimir: A44
Kerpal, Christian: HT7
Khanna, Shiv N.: INV7
Kickermann, Andreas: HT19
Kiermaier, Josef: A71
Kikuchi, Hayato: B35
Kimoto, Koji: HT12
Kimura, Katsuya: B13
King, R. Bruce: B50
Kinoshita, Naoya: B86
Kirilyuk, Andrei: HT17, A9, A21, B2, B26, B52
Kitagawa, Hiroshi: A25
Kitajima, Kensei: B60
Kitazumi, Kosuke: B44
Kler, Rantej: HT12
Knall, Florian: A32
Knoller, Fabian: B68
Kobayashi, Hikaru: B13, B16
Kobayashi, Hirokazu: A25
Kobayashi, Keita: B3
Kobayashi, Naoki: HT13, B62
Koç, Mumin M.: B39, B88
Kodama, Takeshi: B34
Koga, Hiroaki: B70
Kohara, Kei: B72
Koivisto, Jaakko: A8, A10, A37, B45
Koizumi, Hiroki: B35
Kojima, Takao M.: A61, B61
Komukai, Tatsuya: B46, B64
König, Michael: B68
Konishi, Katsuaki: HT13, A27, A57, B62
Kono, Naoko: A43
Koretsune, Takashi: HT8
Koshizaki, Naoto: B19
Kossick, Martin: B9
Koyama, Kohei: A81

Koyasu, Kiichirou: A26, A30, A79, B22, B23,
B59, B74, B79
Kresin, Vitaly: HT4
Kreutzer, Johannes: B36
Krikunova, Maria: HT19, A5
Krstic, Marjan: B66
Kubota, Yoshiki: A25
Kuhn, Martin: INV5
Kumada, Takayuki: A6
Kumar, Vijay: HT1, A50, A72
Kümmel, Stephan: B9
Kupiainen-määttä, Oona: B15
Kurashige, Wataru: A35, A60, A64
Kurawaki, Junichi: A40, B25
Kurihara, Takuya: A59, B53
Kurtén, Theo: B15
Kvashnina, Kristina: B24
Kwak, K: B18
Laarmann, Tim: HT19
Lahtinen, Tanja: A8, A10, A37, B45
Lalanne, Matthieu: HT5
Lang, Johannes: HT25
Lang, Sandra M.: B66, B82
Langbehn, Bruno: B10
Langenberg, Andreas: B9, B10
Larsson, J. Andreas: B31
Lau, Tobias: B9, B10, HT22, HT25
Lawicki, Arkadiusz: HT22, HT25, B9
Lebon, Alexandre: A22
Lee, D: B18
Lei, Meng: B12
Leisner, Thomas: INV6
Leppert, Linn: B9
Li, Houhua: A49, A73
Li, Yejun: A44
Li, Yunguo: B31
Li, Zhe: B6
Liang, Anthony: HT4
Liang, Xiaoqing: HT21, B51
Liao, Kaiming: A38
Lievens, Peter: INV18, B6, B8, B11, B24
Litcarev, Misha: A21
Liu, Jian: A74
Llorca, Jordi: A49
Logemann, Remko: B52

Lopez, Maria J: HT20
Lopez-acevedo, Olga: A1
López-lozano, Xóchitl: HT11, B18
Loukonen, Ville: B15
Lu, Shengjie: HT21
Lyalin, Andrey: HT15, A75, A78, B73, B75
Lyon, Jonathan T.: HT7
Maeda, Masanori: B16
Maeda, Satoshi: A55, A78, B75
Mafuné, Fumitaka: HT23, A76, A81, A86, B83
Maity, Prasenjit: A48
Majima, Takuya: B60
Malola, Sami: A8, A10, A37, B45
Marjomäki, Varpu: A37
Mårsell, Erik: A13
Martikainen, Mari: A37
Martinez, Franklin: HT24, B37
Maruyama, Shigeo: A82, B80
Marx, Gerrit: HT24, B37
Masuda, Tomohide: A36
Matsuami, K.: A4
Matsuda, Aya: A28, A29
Matsumoto, Jun: A43
Matsumoto, Taketoshi: B13, B16
Matsunami, Kenji: A15
Matsuzaki, Miku: A31
Matsuzawa, Hidenori: B41
Mazet, Clément: A49, A73
Mcnally, Mike J.: A3, B39, B88
Meijerink, Andries: B14
Meinen, Jan: INV6
Meiwes-Broer, Karl-Heinz: INV17, B89
Melis, Claudio: INV14
Metha, Gregory: HT12
Meyer, Jennifer: HT25
Mi, Wenbo: B1
Mikkelä, Mikko-Heikki: HT2, A13
Milani, Paolo: INV14
Miron, Catalin: A4
Misaizu, Fuminori: A14, A88, B46, B57, B64
Mise, Yoshiyuki: B81
Miyajima, Ken: HT23, A76, A81, A86, B83
Miyasaka, Mitsuru: B81
Miyawaki, Jun: A63
Miyazaki, Kasumi: A29

Moeller, Thomas: INV17
Möller, Thomas: HT19, A5, B9, B10
Mondal, Subhendu: A4, A15Mori, Hirotoshi: A28, A29
Morita, Keisuke: A86
Morita, Takeshi: B48
Moriyama, Ryoichi: A88, B46, B57, B64
Morokuma, Keiji: INV2
Motomura, Koji: A4, A15
Müller, Jan-Phillipe: A5
Muller, Maria: HT19, A5
Murakami, Junichi: A77
Murakami, Ryohei: A65
Muramatsu, Satoru: B59
Mustalahti, Satu: A8, A10
Myllyperkiö, Pasi: A10
Nachbar, Mario: INV6
Nagao, Kyohei: B30
Nagasawa, Hiroshi: B30
Nagase, Tomomi: A58, B56
Nagashima, Umpei: A77
Nagasono, M.: A15
Nagata, Toshiaki: HT23, B83
Nagaya, Kiyonobu: A4, A15
Nakai, Yoichi: A61, B61,
Nakajima, Atsushi: A20, A23, A58, B38, B56
Nakajo, Erika: A36
Nakao, Yukimichi: A77
Nakashima, Naotoshi: A39, B21
Nakashima, Yukinori: B47
Nakatake, Daiki: A80
Nakaya, Masato: B38
Nakayama, Akira: HT15, B73
Nakayama, Tomonobu: HT12
Nande, A.: INV15
Nanjyo, Hiroki: B86
Neeb, Matthias: HT16
Negishi, Yuichi: A31, A35, A60, A64, B85
Nicolas, Christophe: A4
Niedner-schatteburg, Gereon: HT25
Niemeyer, Markus: B10
Niidome, Yasuro: A39, B21
Niiori, Yoshiki: A31
Nishi, Nobuyuki: A46
Nishi, Teppei: B44

Nishida, Naoki: A87, B84, B86
Nishigaki, Jun-Ichi: A48
Nishikawa, Keiko: A51, B48
Nishio, Tatsuya: B60
Nishiyama, Toshiyuki: A4, A15
Nobusada, Katsuyuki: A35, A64
Noda, Yasuto: A59, B53
Noda, Yusuke: B33
Nojiri, Kazunari: B3
Nonose, Shinji: A67
Nösel, L.: HT19
Odaka, Hideho: B87
Oelze, T.: HT19
Ogasawara, Kazuki: A82, B80
Ohashi, Hironori: A84, B81
Ohashi, Kazuhiko: A46
Ohno, Kaoru: A83, B33
Ohshima, Takashi: A80
Ohshimo, Keijiro: A14, A88, B46, B57, B64
Ojanperä, Ari: A1
Okamoto, Koichi: A41
Okamura, Hiroaki: A40, B25
Okumura, Mitsutaka: A84, B70
Okutsu, Kenichi: A14
Olenius, Tinja: B15
Onitsuka, Satoaki: A40
Ono, Akira: B29
Ono, Shota: B33
Ono, Yuriko: A55, B75
Onoe, Jun: HT9
Onoe, Kaoru: B41
Oonishi, Yoshiki: B60
Oulevey, Patric: A7
Ovcharenko, Yevheniy: HT19
Pacchioni, Gianfranco: B6Pahl, Elke: B49
Palmer, Richard E.: INV1, A74
Peeters, Francois M.: B8
Pelayo, J. Jesús: HT6
Peltz, Christian: INV17
Peng, Dongliang: B1
Peng, Dong-Liang: B12
Peredkov, Sergey: HT16
Pérez, Daniel: B8
Pérez, Luis: HT6

Pérez, Luis Antonio: B69
Peters, Lars: A21, B2Peters, Sven: HT16
Pettersson, Mika: A8, A10, A37
Pham, Thi Nu: A83
Picot, Thomas: B8, B11
Podestà, Alessandro: INV14
Polak, Wieslaw: B42
Postler, Johannes: INV5, A45
Probst, Michael: A45
Przystawik, Andreas: HT19
Ptasinska, Sylwia: B27
Puska, Martti: A1
Qin, Yuyuan: B40
Raebiger, Hannes: B5
Ralser, Stefan: INV5, A45
Ramakrishna, Guda: B18
Rasing, Theo: HT17, A21, B26
Ravagnan, Luca: INV14
Renzler, Michael: INV5
Richter, Robert: B9
Rittmann, Jochen: B9
Roberts, Sloan: INV9
Roeffaers, Maarten: B24
Rohrmann, Urban: HT26
Rosén, Arne: A24, B4, B31
Rüffer, Rudolf: B8
Rupp, Daniela: INV17, HT19, A5
Ruzicka, Jan-Yves: HT12
Ryuzaki, Sou: A41
Saito, Makoto: A82, B80
Saito, Norio: A15
Saito, Susumu: HT8
Sakai, Tsukasa: A4, A15
Sakamoto, Masanori: B55, B58
Sakata, Kohei: A84, B70
Salazar, Fernando: HT6
Salorinne, Kirsi: A8, A10, A37, B45
Sameh, Kaziz: A49, A73
Sanyal, Biplab: A21, B2
Sarugaku, Shun: A16, A65
Sasaki, Jun: A46
Sato, Yoshinori: A82, B80
Sattar, A.: INV15
Sauceda, Huziel E.: HT6, A54

Sauer, Joachim: A69
Saupe, M: INV17
Sauppe, Mario: HT19, A5
Sawakami, Isao: A59
Schaal, C.: B89
Schäfer, Rolf: HT26, A2, B43
Scheier, Paul: INV5, A45, B63
Schöllkopf, Wieland: A69
Schooss, Detlef: INV16
Schorb, Sebastian: HT19, A5
Schouteden, Koen: B6
Schroedter, Lasse: HT19
Schropp, Ruud: B14
Schubert, Ulrich: B36
Schwaneberg, Falko: HT5
Schwarz, Ulrike: INV16
Schweikhard, Lutz: HT24, B37
Schwerdtfeger, Peter: HT26, B43, B49
Sekiya, Hiroshi: A46
Sels, Bert: B24
Shayeghi, Armin: A2, B43
Shibuta, Masahiro: A23
Shichibu, Yukatsu: HT13, A27, A57, B62
Shimamoto, Daisuke: B71
Shimaya, Atsushi: B35
Shiraishi, Chihiro: A47
Shiromaru, Haruo: A43, B34
Shu, Haibo: HT10
Skruszewicz, S.: B89
Smith, A.: INV15
Song, Fengqi: B40
Song, Xiaowei: HT5, A69
Stanca-kaposta, Cristina: HT5
Steenbergen, Krista G.: HT3
Stock, David: INV5
Su, Yan: B50
Suga, Shoichiro: B56
Sugai, Toshiki: A82, B35, B80
Sugawara, Ko-Ichi: A63
Sugawara, Yoshito: A58
Sugiuchi, Mizuho: B62
Suzuki, Hiroki: A12
Suzuki, Shinzo: B29, B30
Tachibana, Tetsuya: A4, A15
Tada, Kohei: B70

Taguchi, Yuki: B34
Tahara, Hiroshi: A88, B57
Takahashi, Masao: B13
Takahashi, Naoko: B44
Takahashi, Yukina: B25
Takahata, Ryo: B23
Takano, Shinjiro: A60, A79, B22
Takegawa, Ryuich: A40
Takegoshi, Kiyonori: A59, B53
Takemura, Koichi: A47
Takenouchi, Masato: A76
Taketsugu, Tetsuya: HT15, A55, A75, A78,
B73, B75
Takiya, Toshio: A62
Tamada, Kaoru: INV10, A41
Tanaka, Hideki: A87, B84, B86
Tang, Wingjohn: HT14, B14
Taniguchi, Masateru: A41
Tano, Kensuke: A4
Tanuma, Hajime: A43
Tarras-wahlberg, Nils: B4
Tchaplyguine, Maxim: HT2, A13
Temst, Kristiaan: INV15, B8, B11
Terada, Katsuhide: B35
Terai, Tomoyuki: B3
Teranishi, Toshiharu: B55, B58
Terasaki, Akira: HT22, HT25, A16, A17, A53,
A65, B10, B72, B9
Terry, William D: A74
Thanthirige, V. D.: B18
Tiggesbäumker, J.: B89
Tobari, Yuta: A82, B80
Tobita, Kenichiro: A16, A17
Togashi, Tadashi: A15
Tokunaga, Makoto: A84, B81
Tolbatov, Iogann: B27
Toleikis, Sven: HT19
Tombers, Matthias: HT25
Torricelli, Gauthier: B39, B88
Trekels, Maarten: B8
Treusch, Rolf: A5
Trioni, Mario I.: B6
Tschurl, Martin: A71
Tsuchida, Hidetsugu: B60
Tsuji, Masaharu: A47, B19, B47, B71

Tsuji, Takeshi: B19
Tsuji, Tetsuro: B81
Tsukuda, Tatsuya: A26, A30, A48, A60, A64,
A79, B22, B23, B59, B74, B79
Tsunoyama, Hironori: A58, B38, B56
Uchida, Chihiro: A31
Ueda, Hiroki: B60
Ueda, Kiyoshi: A4, A15
Ueno, Eri: A62
Umemoto, T.: A4
Umezu, Ikurou: A62
Uosaki, Kohei: HT15, B73
Urushizaki, Masaru: A79
Uto, Keiko: A47
Vaida, Mihai E.: A32
Van Bael, Margriet J.: INV15, B8, B11
Van Blaaderen, Alfons: HT14, B14
Van Dijk, Chris: B2
Van Haesendonck, Chris: B6
Van Huis, Marijn: B14
Vantomme, Andre: B8, B11
Varnholt, Birte: A7
Vass, Albert: HT24, B37
Vega, Andrés: A22
Vehkamäki, Hanna: B15
Vogel, Marlene: B9
Von Haeften, Klaus: A3, B39, B88
Von Issendorff, Bernd: INV4, HT22, HT25,
A22, B9, B10
Von Weber, Alexander: INV9
Vonderach, Matthias: INV16
Wada, Shin-Ichi: A4, A15
Wada, Yoriko: A6Wågberg, Thomas: B31
Wakabayashi, Tomonari: A6, B34
Wan, Jian-guo: B32
Wang, Da: B14
Wang, Guang-hou: A38, B32, B40
Wang, Huan: B11
Wang, Jue: A38
Wang, Jun-Bao: B1, B12
Wang, Lai-Sen: B1, B12
Watanabe, Naoki: A61, B61
Watanabe, Tomomi: A30
Watanabe, Yoshihide: A70, B44

Watkins, Mark: A3, B39, B88
Weis, Patrick: INV16
Weissker, Hans-Christian: HT11, B18
Whetten, Robert L.: B18
Wiebke, Jonas: B49
Winbauer, Andreas: A71
Winghart, Marc-Oliver: INV16
Wodka, Dawid: A49, A73
Wolke, Conrad: HT25
Wolter, David: HT19, A5
Wöste, Ludger: HT5
Wu, Jenna W. J.: A88, B57
Xu, Hong-Guang: HT21, B51
Xu, Weiqing Q.: A4Xu, Ziwei: HT10
Yabashi, Makina: A4, A15
Yabushita, Satoshi: A36
Yaga, Minoru: A62
Yajima, Atsuhiko: A47
Yamada, Sunao: B25
Yamaguchi, Masaki: A35
Yamamoto, Gun: A46
Yamamoto, Takayuki: A25
Yamamoto, Yasushi: B81
Yamanaka, Shusuke: B70
Yamauchi, Miho: B76
Yamazaki, Kenichiro: A14
Yamazoe, Seiji: A60, A64, A79, B22, B23,
B59, B79

Weinberger, Nikolaus: B63
Yanagimachi, Akimaro: B74
Yao, Makoto: A4, A15
Yase, Satoshi: A15
Yasuda, Hidehiro: B3
Yasumatsu, Hisato: A32, A56, B67
Yazaki, Ryo: A80
Yazdanfar, Hanieh: A3, B39, B88
Yin, Feng: A74
Yokote, Yuki: A80
Yokoyama, Takushi: A84, B81
Yonemura, Mari: B84
Yoshida, Daisuke: B5
Yoshimura, Kazuki: A77
Yoshizawa, Kazunari: HT18
Youle, Oliver: B39, B88
Yu, Yingying: A11
Yuan, Qinghong: HT10
Zamudio-bayer, Vicente: HT22, HT25, B9, B10
Zhang, Bei: A49, A73
Zhang, Chaofan: HT2, A13
Zhang, Mingzhe: A27, A57
Zhang, Qinfu: B1
Zhang, Xiuyun: HT10
Zhao, Jijun: HT21, B50, B51
Zheng, Weijun: HT21, B51
Zou, Chen-Yang: B12

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