Abstracts of Poster Presentations,Sep. 3249

3PP-01

Exact two-component relativistic theory for NMR parameters
1

Qiming Sun, Wenjian Liu, Yunlong Xiao
College of Chemistry and Molecular Engineering, Peking University
Abstract

The calculation of Nuclear magnetic resonance (NMR) shielding constants demands fully relativistic treatments since they are sensitive to the electronic structurein the vicinity of the nucleus. Following the exact two-component (X2C) relativistic theories for electronic structure [1–5], a simple X2C theory for NMR shielding constants is proposed [6]. With the so-called magnetically balanced (MB) basis sets [7–10], a matrix decoupling condition is introduced to reduce the fourcomponent formalism down to the two-component one. The inclusions of GIAO
via the MB-GIAO scheme [11] and the Gaunt term for current-current interaction
are available. In the X2C approximation, the dia- and para-magnetic terms, which
are identical to the corresponding four-component ones, arise naturally. The extra
computational effort is inevitable since the coupled-perturbed equations are required
not only for the molecular orbitals but also for the decoupling procedure. However,
the efﬁciency can be gained by introducing the concept of “from atoms to molecule”.
Both the exact and approximate schemes will be examined at the DFT level.

References[1] W. Kutzelnigg and W. Liu J. Chem. Phys. 2009, 123, 241102.
[2] D. Peng, W. Liu, Y. Xiao and L. Cheng J. Chem. Phys. 2007, 127, 104106.
[3] W. Liu and W. Kutzelnigg J. Chem. Phys. 2007, 124, 114107.
[4] W. Liu and D. Peng J. Chem. Phys. 2009, 131, 031104.
[5] W. Liu Mol. Phys. 2010, 108, 1679.
[6] Q. Sun, W. Liu, Y. Xiao, and L. Cheng J. Chem. Phys. 2009, 131, 081101.
[7] Y. Xiao, D. Peng, and W. Liu J. Chem. Phys. 2007, 126, 081101.
[8] Y. Xiao, W. Liu, L. Cheng and D. Peng J. Chem. Phys. 2007, 126, 214101.
[9] W. Kutzelnigg and W. Liu J. Chem. Phys. 2009, 131, 044129.
[10] L. Cheng, Y. Xiao, and W. Liu J. Chem. Phys. 2009, 130, 144102.
[11] L. Cheng, Y. Xiao, and W. Liu J. Chem. Phys. 2009, 131, 244113.

250

3PP-02

4XDQWL]DWLRQRI&KHPLFDO5HDFWLRQ7KH'\QDPLF&RUUHODWLRQ'LDJUDP0HWKRG)UHHIURP1RQFURVVLQJ5XOH
+LUR\XNL1RKLUD 7RVKL\XNL1RKLUD

3URIHVVRU(PHULWXVIURP6DLWDPD8QLYHUVLW\-DSDQ*UDGXDWH6FKRRORI(QHUJ\6FLHQFH.\RWR8QLYHUVLW\-DSDQ%RWK )XNXL¶V IURQWLHU RUELWDO )2  WKHRU\ >@ DQG :RRGZDUG+RIIPDQQ¶V RUELWDO
V\PPHWU\ FRQVHUYDWLRQ :+  WKHRU\ >@ DUH EDVHG RQ WKH PROHFXODU RUELWDO 02 WKHRU\ +RZHYHU WKHUH DUH VRPH REYLRXV LQFRQVLVWHQFLHV EHWZHHQ WKH WZR WKHRULHV LQ
H[SODLQLQJ WKH HOHFWURQ PRYHPHQW >@ 7KH SURFHVV RI FKHPLFDO UHDFWLRQV KDV EHHQ
H[SODLQHG E\WKHSRWHQWLDOVXUIDFHDQDO\VLV EDVHG RQWKHWLPHLQGHSHQGHQW6FKU|GLQJHUHTXDWLRQ +RZHYHU WKLV DSSURDFK LV QRW DOZD\V DSSURSULDWH IRU GHVFULELQJ XQVWHDG\VWDWHV EHFDXVH WKH YDULDEOH RI UHDFWLRQ FRRUGLQDWH VKRXOG EH WLPH W E\ LWV YHU\ QDWXUH
:KHQFRQVLGHULQJWKHWLPHVFDOHRIFKHPLFDOUHDFWLRQV IRUPROHFXOHVWKHUH LV LQKHUHQWXQFHUWDLQW\LQWKHHQHUJ\OHYHOVIRUWKHPLGZD\VWDWHRIFKHPLFDOUHDFWLRQVRZLQJWRWKH
+HLVHQEHUJXQFHUWDLQW\SULQFLSOH>)LJ@7KHVWDWHVZKLFKFDQEHDFFXUDWHO\GHVFULEHG
E\ TXDQWXP PHFKDQLFV H[LVW GLVFRQWLQXRXVO\ LQ FKHPLFDO UHDFWLRQV 6XFK TXDQWL]DWLRQRI FKHPLFDO UHDFWLRQV VROYHV DOO QRQFURVVLQJ SUREOHPV :H DOVR VKRZ WKDW VXFK DQ
HVVHQWLDO IDFW OHDGV WR QHZ FRQFHSWV DQG WKHRULHV LQ FKHPLFDO UHDFWLRQV VXFK DV VWDEOH
PROHFXOH HOHPHQWDU\ UHDFWLRQ PLQLPXP GHIRUPDWLRQ RI RUELWDO SKDVHV DQG WKHXQLYHUVDOO\ DSSOLFDEOH ³G\QDPLF FRUUHODWLRQ GLDJUDP PHWKRG´ XQLI\LQJ )2 WKHRU\ DQG:+WKHRU\>@ 
7KHRULJLQDO6FKU|GLQJHUHTXDWLRQ      ­ ! 
½
w< U  W
L!
  9 U  W ¾< U  W 
®
wW
¿
¯ P

%RUQ2SSHQKHLPHUDSSUR[LPDWLRQ   6HSDUDWLRQRIWKHYDULDEOHUIURPW      $VVXPSWLRQRIVWDWLRQDU\VWDWHV
7KHUHVXOWLQJWLPHLQGHSHQGHQWHTXDWLRQ
­ ! 
½
  9 U ¾< U ( < U 
®

¿
¯ P
)LJ  $ VFKHPDWLF UHSUHVHQWDWLRQ RI WKH
SRWHQWLDO HQHUJ\ VXUIDFH DQG WLPH FRXUVH IRUDQHOHPHQWDU\UHDFWLRQ>@)XNXL.$FF&KHP5HV
>@:RRGZDUG5%+RIIPDQQ57KH&RQVHUYDWLRQRI2UELWDO6\PPHWU\
9HUODJ$FDGHPLF:HLQKHLP*HUPDQ\>@1RKLUD+7HWUDKHGURQ/HWW
>@1RKLUD+7KHVW,83$&:RUOG&RQJUHVV627RULQR,WDO\251

3PP-03

Additional variational condition in the ROHF method
ensuring a fulfillment of Koopmans’ theorem
Boris N. Plakhutin 
Laboratory of Quantum Chemistry, G.K.Boreskov Institute of Catalysis,
Russian Academy of Sciences, Novosibirsk 630090, Russia. A general formulation of Koopmans’ theorem (KT) is derived in the ROHF method for
molecular and atomic systems with arbitrary orbital occupancies and total electronic
spin. The key point of the formulation is the new variational condition introduced in
the ROHF method in addition to the familiar variational principle for the total energy.
The new condition ensures the stationarity of the ionized energy (ionization potential orelectron affinity) defined in Koopmans’ approximation with respect to a variation oforbitals within the ionized electronic shell. Taken together, the variational principle
and the new condition define the special (canonical) form of the ROHF Hamiltonian
whose eigenvalues (orbital energies) satisfy KT for the whole energy spectrum.
The talk will focus on an intimate relation between the variational conditions underlying the present (canonical) ROHF method and the variational conditions in the limited C I approach, and on a practical applicability of the new theory.
KT estimates [4] of the valence ionization potentials of the second row
open-shell atoms. Basis set aug-cc-pV6Z. All values in eV.
I 2 s , KT

I 2 s , experim.

5.342
8.415

5.39189.32270

I 2 p , KT

I 2 p , experim.

Li2

S , 2s1

Be

1

2

B

2

P , 2 p1

12.222

12.93

8.432

8.2981

C

3

P , 2 p2

16.082

16.59

11.792

11.260N

4

S , 2 p3

20.11820.33

15.44514.53414O3

P , 2 p4

29.57628.48

14.452

13.618F

2

P , 2 p540.36537.86

18.62117.423S , 2s

1. B.N. Plakhutin, E.V. Gorelik, and N.N. Breslavskaya, J. Chem. Phys. 125, 204110(2006).
2. B.N. Plakhutin and E.R. Davidson, J. Phys. Chem. A. 113, 12386 (2009).
3. E.R. Davidson and B.N. Plakhutin, J. Chem. Phys. 132, 184110 (2010).
4. B.N. Plakhutin, submitted.




252

3PP-04

The electronic propertiesof organic dyes porphyrin-thiophene-perylene
and its derivatives modified by varying thiophene linker
Tatiya Chokbunpiam,1,2 Patchanita Thamyongkit,3 Oraphan Saengsawang,2Supot Hannongbua2,41

Petrochemical and Polymer Science Program, Faculty of Science, Chulalongkorn
University, Bangkok, 10330, Thailand

2

Computational Chemistry Unit Cell (CCUC), Department of Chemistry, Faculty of
Science, Chulalongkorn University, Bangkok, 10330, Thailand

3

Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok,
10330, Thailand

4

Center of Excellence for Petrochemicals, and Advanced Materials, Chulalongkorn
University, Bangkok, 10330, Thailand.

Abstract
In this work, quantum chemical calculation was applied to investigate a new series ofpotential light-harvesting compounds consisting of porphyrin molecule linked toperylene unit via a oligothiophenic bridge (Por-nThio-Per). The number (n) of
thiophene ring was varied from 0 to 10 rings. Electronic properties of these compounds
were studied using density functional theory (DFT) and time-dependent DFT approaches.
The results revealed that Por-3Thio-Per compound can be a new promising compound
which acts as light harvesting in organic dye solar cell. Due to, this compound display
sufficient performance in terms of band energy, molecular orbital coefficient andUV-visible spectra covered a broader range without disturbing characteristic spectra ofchromophor.

Figure 1. Molecular structure of Por-nThio-Per (n = 010).
Reference>1] M. Gräzel, J. Photochem. Photobiol.A, 2004, 164, 3-14.
>2] H. Hoppe and N. S. Sariciftci, J. Mater. Res., 2004, 19(7), pp. 1924-1944.

253

3PP-05

FRANCK-CONDON FACTORS FOR DIATOMIC
MOLECULES FOR AN ARBITRARY ANHARMONICPOTENTIAL

L. SANDOVAL1 , I.URDANETA2 , and A. PALMA2
1 Facultad de Ciencias de la Computación, Benemérita Universidad Autónoma

de Puebla. Puebla, Pue. 72570 (lourdes.sandoval55@gmail.com)
2 Instituto de Fı́sica, Benemérita Universidad Autónoma de Puebla. Puebla,

Pue. 72570 (palma@sirio.ifuap.buap.mx), (urdaneta@sirio.ifuap.buap.mx)
Abstract
In this work we develop a harmonic approximation of the FranckCondon Factors (FCF) for any anharmonic potential of diatomic molecules.
The method is based on the Taylor series expansion of the potential andthe second quantization formalism. Well known recurrence relations
are used to calculate the FCF, which are incorporated in the hamiltonian. Keeping then only the quadratic terms, by the BogoliubovTyablikov transformation the hamiltonian is found to be equivalent toan harmonic oscillator. The derivation is an alternative route to the
Iterative Bogoliubov transformation (IBT), widely used to treat anharmonic potentials in a non-perturbative way. The FCF obtained byour method for the Morse potential are compared with numerical techniques like the RKR method and the Morse itself. Our results are inagreement with these numerical methods, being our technique entirely
analytical and much simpler to use.

254

3PP-06

Faddeev Random Phase Approximation for Molecules
Matthias Degroote,1 Dimitri Van Neck,1 Carlo Barbieri2
1
Center for Molecular Modelling, Ghent University, Belgium
2
University of Surrey, United Kingdom
The Faddeev Random Phase Approximation (FRPA) [1,2] is a Green’s function
method which couples collective degrees of freedom to the single particle motion by
resumming an inﬁnite number of Feynman diagrams. The Faddeev technique is applied to describe the two-particle-one-hole (2p1h) and two-hole-one-particle (2h1p)
states in terms of Random Phase Approximation (RPA) phonons. This results inan equal treatment of the intermediary particle-particle (pp) and particle-hole (ph)channels. The poster will present the application of this method to molecules [3]and investigate the eﬀects of adding fragmentation to the single particle propagatoron the RPA instability arising in the dissociation limit.
[1] C. Barbieri and W. H. Dickhoﬀ, Phys. Rev. C 63, 034313 (2001)[2] C. Barbieri, D. Van Neck and W. H. Dickhoﬀ, Phys. Rev. A 76, 052503 (2007)[3] M. Degroote, D. Van Neck and C. Barbieri, Phys. Rev. A 83, 042517 (2011)255

3PP-07

Development and applications of divide-and-conquer constrained
self-consistent field method
Minoru Hoshino,1 Yutaka Imamura,2 Masato Kobayashi,2,3 Hiromi Nakai2,4,5
1
Nissan Chemical Industries, LTD., Japan
2
School of Advanced Science and Engineering, Waseda University, Japan
3
Institute for Molecular Science, Japan
4
Research Institute for Science and Engineering, Waseda University, Japan
5
CREST, Japan Science and Technology Agency, Japan
I. Introduction
The evaluation of Marcus parameters1 such as a reorganization energy and anelectron coupling matrix is essential for the analysis of electron transfer (ET) processes
in electronic materials and biological systems. Recently, Wu et al.2 developed theconstrained self-consistent field (CSCF) method to obtain the charge- and spin-localized
diabatic states in the ET process within the framework of density functional theory andestimated the Marcus parameters including donor-acceptor interactions. The
computational cost of the CSCF method scales as O(n3–4), which is the same as that of
the conventional SCF method, with the prefactor of the determination steps for
Lagrange multipliers.
Nakai and coworkers3,4 have developed the divide-and-conquer (DC) method as alinear-scaling approach. The DC method can accelerate the diagonalization andconstruction of the Fock matrix and achieves linear-scaling computational cost for the
SCF and correlated methods. This study has developed the hybrid approach between the
DC and CSCF methods to deal with large-scale ET systems.
II. DC-CSCF theory
The DC method divides the entire system into small subsystems D composed ofcentral and buffer regions. The total energy is described by
1 n ,pE DC(1)¦¦ ¦ DPQVD H PQcore  FPQV .
2 D V PQ L (D )The density matrix of the subsystem DDis constructed from subsystem orbitals, theFermi function fE, and the partition matrix pD:
VD
D
(2)
DPQ
pPQ
¦ f E (H FV  H iVD )CPVDi CQVDi * .
i

The CSCF Lagrangian based on the DC expression is given byª n ,pº
VD(3)
W DC E DC  ¦ VI «¦¦ ¦ DPQ
IP Oˆ IV IQ  N IV » .
I¬ D V PQ L (D )¼
The second term on the right-hand side in Eq. (3) represents the constraint conditions
with the Lagrange multipliers VI. The equations derived from the differentiations of the
CSCF Lagrangian with respect to the orbitals and multipliers are solved
self-consistently in the DC scheme.
The DC-CSCF method has been implemented to the DC part5 in the GAMESS
program. Applications to the organic semiconductor materials will be reported in thispresentation.
1
R. A. Marcus and N. Sutin, Biochim. Biophys. Acta 811, 265 (1985). 2Q. Wu and T. V. Voorhis, Phys. Rev. A 72,
024502 (2005). 3T. Akama, M. Kobayashi, and H. Nakai, J. Comput. Chem. 28, 2003 (2007). 4M. Kobayashi, T.
Yoshikawa, and H. Nakai, Chem. Phys. Lett. 500, 172 (2010). 5M. Kobayashi and H. Nakai, in Linear-Scaling
Techniques in Computational Chemistry and Physics: Methods and Applications, edited by M.G. Papadopoulos, R.
Zalesny, P.G. Mezey, and J. Leszczynski (Springer, 2011), pp. 97-127.

256

3PP-08

Gauge Function Optimization for Accurate Calculations of Magnetic
Wavefunctions
Atsushi Kubo
Division of Chemistry, Graduate School of Science,
Kyoto University, Kyoto 606-8502 Japan
In this poster, we will present some of the results discussed in our recent papers.
[1,2] In the first paper, we showed that our computed current density for a H2+GionG in avery strong magnetic field (1 a.u.) did not satisfy the continuity equation,   J 0 .
Epstein had noticed such violation of the conservation law and had tried to cure it[3].
We applied the Kennedy-Kobe (KK) variational principle to remove the divergence.[4]This method was only applied to an anisotropic harmonic oscillator, but has never been
applied to real molecular systems.
In the second paper, we discussed about the difference between the gauge function
optimization and the gauge invariant methods by Rebane[5] and by Lazzeretti and his
coworkers[6]. The original paper was modified according to the suggestion of areviewer to include the latter references. After the change, the manuscript became moreclear. We thank the reviewer for helping us. The gauge invariant method adopts therandom phase approximation, since the exchange term is nonlocal and is notgauge-invariant.[3a] On the contrary, we can combine the Hartree-Fock approximation
with the gauge function optimization to remove the error. Moreover, in the gauge
function optimization, the basis sets have to be optimized only for electron density,
since a part of electron velocity field is described by the gauge function. Therefore, thesize of the basis sets might be reduced.
We also investigated the case where the wavefunction had nodes. It has been known
that the Rebane's equation is problematic at the nodes [6c] . The second paper showedthat the KK equation can be solved without any problem. We confirm that the algorithm
is correct, although we still do not know whether the method is effective or not.
However, we believe that science has been developed from something unknown rather
than the competition for a known subject.
[1] Atsushi Kubo, "Finite-element gauge function optimization for accurate current
density calculations", Phys. Rev. A80, 032117 (2009).
[2] Atsushi Kubo, "Gauge Function Optimization 2: An accurately solvable model.", Int.
J. Quantum Chem. accepted on 11 May 2011.
[3](a) S.T. Epstein, JCP 42, 2897 (1965); (b) JCP 58, 1592 (1973); (c) Isr. J. Chem. 19,
154 (1980).
[4] P.K. Kennedy and D.H. Kobe, Phys. Rev. A 30, 51 (1984).
[5] T.K. Rebane, Sov. Phys. JETP 11, 694 (1960).
[6](a) P. Lazzeretti, et al. Int. J. Quantum Chem. 60, 249 (1996). (b) M.P. Beccar Varela,
et al. ibd. 77, 599 (2000). (c) S. Pelloni, et al., J. Phys. Chem. A 113, 14465 (2009).

257

3PP-09

Relativistic Corrections via Fourth-Order Direct Perturbation
TheoryStella Stopkowicza) and Jürgen Gauss a)a) Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz, Germany

Relativistic effects need to be considered in quantum-chemical calculations on systems including heavy elements or when aiming at high accuracy for molecules containing
only lighter elements. For the latter purpose, consideration of relativistic effects via perturbation theory is an attractive option, and consequently such techniques, e.g., lowestorder direct perturbation theory (DPT2) [1] have evolved to standard tools for the calculation of relativistic corrections to energies and properties.
In this work, we extend the DPT treatment to the next order (DPT4) and demonstratethat the DPT4 energy correction can be obtained as a second derivative of the energy respect to the relativistic perturbation parameter. Accordingly, differentiation of a suitable
Lagrangian, thereby taking into account all constraints on the wavefunction, provides asuitable expression for the fourth-order energy correction. The latter can be implemented
using standard analytic second-derivative techniques. For closed-shell systems, the DPT4
corrections consist of higher-order scalar relativistic effects as well as spin-orbit corrections with the latter appearing here for the first time in the DPT series.
Relativistic corrections are reported for energies as well as for first-order electrical properties and compared to results from rigorous four-component benchmark calculations inorder to judge the accuracy and the convergence behaviour of the DPT expansion.

[1] W. Kutzelnigg, Relativistic Electronic Structure Theory. Part I. Fundamentals, (Elsevier, Amsterdam, 2002), p. 664, chapter 12258

3PP-10Analytic energy derivatives in relativistic quantum chemistry:
Rigorous treatments of both scalar-relativistic and electroncorrelation effects
Lan Cheng and Jürgen Gauss
Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz, Germany

We report on the extension of analytic energy-derivative techniques [1] for quantumchemical computations on heavy-element containing systems. Scalar-relativistic effects
are treated via spin-free relativistic theories including the spin-free Dirac-Coulomb(SFDC) approach [2, 3] in the four-component framework as well as the spin-free exact
two-component (SFX2c) scheme [4, 5].
We present high-level coupled-cluster calculations of various molecular properties
including electric-field gradient, equilibrium geometry, and vibrational frequency anddemonstrate the general applicability of the scalar-relativistic coupled-cluster methods
for systems containing elements from the first down to the fifth row of the periodic
table. It is shown and should be emphasized that scalar-relativistic and electroncorrelation effects need to be treated rigorously on the same footing for accurate
theoretical descriptions, since their contributions are significant and at the same timestrongly coupled together.

[1] I. Shavitt and R. J. Bartlett, Many-Body Methods in Chemistry and Physics: MBPT
and Coupled-Cluster Theory (Cambridge University Press, Cambridge, 2009), Chap. 11.
[2] K. G. Dyall, J. Chem. Phys. 100, 2118 (1994)[3] L. Cheng and J. Gauss, J. Chem. Phys. 134, 244112 (2011)[4] K. G. Dyall, J. Chem. Phys. 115, 9136 (2001)[5] W. Liu and D. Peng, J. Chem. Phys. 131, 031104 (2009)259

3PP-11

Solution of Time Dependent Schr··dinger Equation by Quantum Walk
Shinji Hamada1 Masayuki Kawahata1 and Hideo Sekino1
1
Toyohashi University of Technology, JapanI.

Abstract

Time dependent solution for quantum phenomena is most straightforwardly solved
by Quantum Walk (QW) methods which is natural extension of random walk inclassical statistics. Recently several applications have been performed for the predictionof internal freedom such as electron spin or optical chirality in the context of quantum
computation. We discuss the potential problem of discrete representation QW in solving
time-dependent Schr·dinger equation and present some initial applications forfree-electron and confined electron by potential.
As can be seen below, the solution with periodic condition is completely reproduced bydiscrete QW.

Solution of Time-dependent Schr·dinger Equation with an initial condition ofGaussian distribution260

3PP-12/RFDOXQLWDU\WUDQVIRUPDWLRQLQWZRFRPSRQHQWUHODWLYLVWLFVFKHPHIRUODUJHVFDOHPROHFXODUV\VWHPV-XQML6HLQR +LURPL1DNDL

'HSDUWPHQWRI&KHPLVWU\DQG%LRFKHPLVWU\:DVHGD8QLYHUVLW\ 2NXER6KLQMXNXNX7RN\R-$3$1


5HVHDUFK,QVWLWXWHIRU6FLHQFHDQG(QJLQHHULQJ:DVHGD8QLYHUVLW\ 2NXER6KLQMXNXNX7RN\R-$3$1
&5(67-DSDQ6FLHQFHDQG7HFKQRORJ\$JHQF\6DQEDQFKR &KL\RGDNX7RN\R-$3$1
     5HFHQWO\ 6HLQR DQG +DGD SURSRVHG DQ DFFXUDWH WZRFRPSRQHQW 7&  UHODWLYLVWLF
WKHRU\LQILQLWHRUGHU'RXJODV.UROO ,2'. PHWKRGIRUPDQ\HOHFWURQV\VWHPV>@,Q
WKLV PHWKRG WKH RQHHOHFWURQ 'LUDF +DPLOWRQLDQ DQG HOHFWURQHOHFWURQ &RXORPE
LQWHUDFWLRQ RSHUDWRU DUH WUDQVIRUPHG E\ WKH RQHHOHFWURQ ,2'. XQLWDU\ WUDQVIRUPDWLRQRULJLQDOO\LQWURGXFHGE\ %DU\V]6DGOHM DQG6QLMGHUV %66 >@7KHWRWDOHOHFWURQLF
HQHUJLHV QXPHULFDOO\ DJUHH ZLWK WKRVH REWDLQHG ZLWK WKH IRXUFRPSRQHQW & 
'LUDF&RXORPEPHWKRGHYHQLQVXSHUKHDY\HOHPHQW+RZHYHUIRUODUJHVFDOHPROHFXODUV\VWHPVWKHFDOFXODWLRQIRU7&UHODWLYLVWLF+DPLOWRQLDQFDQEHRQHRIWKHPRVWH[SHQVLYHSDUWVLQWKHWRWDOSURFHGXUHGXHWRWKHXQLWDU\WUDQVIRUPDWLRQLQZKROHPROHFXODUV\VWHP      ,QWKLVVWXG\ZHSURSRVHDQHIILFLHQWDQGDFFXUDWH7&UHODWLYLVWLFVFKHPHEDVHGRQORFDO XQLWDU\ WUDQVIRUPDWLRQ /87  >@ 7KLV VFKHPH XWLOL]HV WKH ORFDOLW\ RI XQLWDU\WUDQVIRUPDWLRQDQGWKHUHIRUHUHGXFHVWKHFRPSXWDWLRQDOVFDOLQJ IURP2 1 WR2 1 ,Q
DGGLWLRQIRUOLQHDUVFDOLQJ+DUWUHH)RFN +) E\7&UHODWLYLVWLFPHWKRGVZHFRPELQH
WKHJHQHUDOL]HGXQUHVWULFWHG+) *8+) ZLWKWKHGLYLGHDQGFRQTXHU '& PHWKRG>@,QWKLVSUHVHQWDWLRQZHZLOOGLVFXVVWKHHIILFLHQF\DQGDFFXUDF\RIWKHVH7&UHODWLYLVWLF
FDOFXODWLRQV >@-6HLQRDQG0+DGD&KHP3K\V/HWW  >@0%DU\V]$-6DGOHMDQG-*6QLMGHUV,QW-4XDQW&KHP  
>@0%DU\V]DQG$-6DGOHM-&KHP3K\V  >@-6HLQRDQG+1DNDLLQSUHSDUDWLRQ>@:<DQJDQG7±6/HH-&KHP3K\V  
>@0.RED\DVKLDQG+1DNDL-&KHP3K\V  

261

3PP-13

Thermoprogrammed reduction and thermoprogrammed desorption
studies of metallic and oxidic catalysts
Vasile Georgescu,1 Fanica Bacalum,2 Luminita Mara3
1
Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy, Spl.
Independentei 202, Bucharest 060041, Romania(vgeorgescu@icf.ro)2
National Institute of Chemistry-ICECHIM , Spl. Independentei 202, Bucharest 060041,
Romania,
3
National Research and Development Institute for Nonferrous and Rare Metals, 102
Biruintei Bvd., Pantelimon, Ilfov, Romania
I.Introduction
Metallic and oxidic catalysts are frequently used in heterogeneous oxidation andreduction, depollution and synthesis of organic compounds.
The investigations of these catalysts requires the determination of the active element
and/or phase, as well as the influence of various factors on the active phase generation.
Among these, an important role is played by the preparation method ( the precursors,
the conditions of calcinations,etc.), the nature of the support as well as its interaction withvarious components, the extent of reduction, etc.
Temperature-programmed reduction (TPR) is developed technique used to chemicallycharacterize of catalysts or catalytic precursors at different stages of the catalyst preparation
sequence.
II.Experimental
During TPR, a hydrogen-containing gas mixture continuously perfuses the catalyst
bed while the temperature of the bed is raised linearly with time. By measuring theconsumption of hydrogen as a function of temperature, a so-called TPR profile is obtained.
The use of such profiles fingerprints of the chemical nature and environment of thecatalytic component. Furtermore, the area under the TPR peak reflects the concentration ofthat component present on the catalyst surface.
Different pretreatments results in different catalytic precursors; the TPR profile is arecord of the reduction of these precursors. It is likely that the precursor pool will contain avariety of species, each with its own characteristic reduction profile. The resulting TPR
spectrum is a composite of these processes with some contribution likely from processes
that do not involve changes in the oxidation state of the metal.
During the TPR process, the oxidation states of the supported metal cations decrease,resulting in a hydrogen consumption. This reduction process ceases after all the reducible
metal cations are consumed..
III Conclusions
The TPR technique is extremely sensitive to the differences between catalysts preparedvia different conditions and to the pretreatments of the catalyst prior to experimentation.
TPR is a temperature-dependent process and calculation equations consists of two
components: an isothermal contribution and a temperature-programmed component.

262

3PP-14

Recent development of the analytic gradient in the fragment
molecular orbital method
Takeshi Nagata,1,2 Dmitri G. Fedorov,2 Kazuo Kitaura1,2
1
Graduate School of Pharmaceutical Sciences, Kyoto University,
46-29 Yoshidashimo Adachi, Sakyo-ku, Kyoto 606-8501, Japan
2
NRI, National Institute of Advanced Industrial Science and Technology (AIST),
1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
Recently, the analytic energy gradient has been shown to be complete at the RHF levelin the framework of the fragment molecular orbital (FMO) method [1], by which theanalytic FMO gradient is applicable to the accurate geometry optimization and themolecular dynamics simulation for large systems. In this study, we present the recent
development of the analytic FMO gradient; the FMO gradient is extended to the MP2level [2] and to consider the solvent effects. Both the explicit and implicit solvent
effects are considered by the effective fragment potential (EFP) method [3,4] and thepolarizable continuum model (PCM) [5,6], respectively. For the latter, a new
FMO/PCM energy expression is proposed, giving a relatively accurate FMO/PCM
energy compared to the previously published expressions [6] and making it easier toformulate and implement the gradient equations. The resulting FMO/PCM gradient wasused to optimize the geometry of the Trp-cage miniprotein construct (PDB ID: 1L2Y)
and the optimized geometry was compared with the first structure in the PDB file. The
RMSD of 0.4136 Å shows that the optimized geometry well reproduces the PDB
structure. We also present the FMO gradient in the electrostatic potential
approximations, which aims for linear-scaling.
[1]. T. Nagata, K. Brorsen, D. G. Fedorov, K. Kitaura, and M. S. Gordon, J. Chem. Phys.
134, 124115 (2011).
[2]. T. Nagata, D. G. Fedorov, K. Ishimura, K. Kitaura, J. Chem. Phys. (in press).
[3]. N. P. Day, H. J. Jensen, S. M. Gordon, and P. S.Webb, J. Chem. Phys. 105, 1968
(1996).
[4]. T. Nagata, D. G. Fedorov, K. Kitaura, and M. S. Gordon, J. Chem. Phys. 131, 024101(2009).
[5]. J. Tomasi, B. Mennucci, R. Cammi, Chem Rev. 105, 2999 (2005).
[6]. D. G. Fedorov, K. Kitaura, H. Li, J. H. Jensen, and M. S. Gordon, J. Comput. Chem.
27, 976 (2006).

263

3PP-15

A perturbation theory for friction of a large particle
immersed in a binary solvent
Yuka Nakamura,1 Akira Yoshimori,1 Ryo Akiyama2
1
Department of Physics, Kyushu University, Japan2
Department of Chemistry, Kyushu University, Japan

F/Fstokes

I. Purpose
We have developed a new theory of a binary solvent to study effects of a
distribution of solvent particles on friction. Here, we consider the friction from solvent
particles to a large solute particle, such as a protein, moving in a solvent. When asolvent consists of two components, the distribution greatly depends on a particle
number ratio of each solvent; hence we can examine effects of a distribution bychanging the ratio. In fact, experiments on actomyosin motors in a binary solvent haveshown effects of a distribution.
II. Theory
We employed a perturbation expansion by assuming that a solvent particle wasmuch smaller than a solute particle. From the expansion, we derived hydrodynamic
equations with new boundary conditions of the surface on a solute particle. By solving
these equations analytically, we expressed the friction by the radial distributionfunctions of a binary solvent. These functions can be calculated from the microscopic
interactions, therefore we can obtain the friction considering the interactions between
solvent and solute particles.
III. Application
Using this theory, we calculated thefriction of a hard-sphere system, varying thesize ratio and mole fraction (Fig.1). The
calculated results showed the large effects of
a distribution on the friction even if a small
EQUQNXGPVUK\G
amount of another component solvent(co-solvent) was added. For instance, thefriction was 1.29 times as large as that of a





one-component solvent when the mole
mole fraction of co-solvent
fraction of a co-solvent was 0.0004 (TheFig.1The friction F calculated by our theory.
ratio of sizes was 50 : 1 : 4). Furthermore,
The vertical axis represents the deviation fromthe deviation from Stokes' law increased with
Stokes' law (slip condition) on F.The size ratio ofa mole fraction of a co-solvent. These
solute, solvent and co-solvent particles is 50 : 1 : X.
tendencies were stronger at a large size of a
X = 2, 3, 4 and 5.
co-solvent than at a small size.

2643PP-16Spin-adapted open-shell TD-DFT
Zhendong Li and Wenjian Liu
Institute of Theoretical and Computational Chemistry, College of Chemistry andMolecular Engineering, Peking University, Beijing 100871, P. R. China
Time-dependent density functional theory (TD-DFT) has emerged as a powerful tool forinvestigating electronic excitations of molecular systems. However, this holds only forclosed-shell systems. As for open-shell systems of unpaired electrons, TD-DFT may failmiserably. On one hand, the results by UKS-based TD-DFT are often severely
spin-contaminated and hence physically meaningless. On the other hand, the standard
ROKS-based TD-DFT can only access those states due to singlet-coupled single
excitations. The missed states due to triplet-coupled single excitations may even belower in energy. The spin-adaption (SA) of TD-DFT sounds at first glanceself-contradictory: The spin-adaption of single excitations require certain double andeven triple excitations but the adiabatic approximation allows only single excitations.
Here we show[1,2] that the way out of this dilemma is to invoke a tensor reference
consisting of all the components of a high-spin multiplet. A minimal yet spin-complete
single excitation configuration space can then readily be constructed by tensor products
between single excitation tensor operators and the tensor reference. Further combinedwith the tensor equation-of-motion formalism, a very compact SA-TD-DFT for
excitation energies can be obtained. Both the implementation and the computation of
SA-TD-DFT are very much the same as the spin-contaminated UKS-TD-DFT. That is,
the elimination of spin-contamination has been achieved for free. The idea of
tensor-coupling is conceptually different from the traditional schemes that takes only
one component of the multiplet as the reference and hence has to invoke ad hoc
redefinitions of excitation operators/levels to generate those higher-rank excitedconfigurations required by spin symmetry.
Reference:
1. Z. Li and W. Liu, J. Chem. Phys. 133, 064106-1-22 (2010).
2. Z. Li, W. Liu, Y. Zhang, and B. Suo, J. Chem. Phys. 134, 134101-1-22 (2011).

265

3PP-17
Assessment of density functional theory for calculations of magnetic interactions ofmanganese complexes
1
Shusuke Yamanaka, Keita Kanda,1 Toru Saito,1 Yasutaka Kitagawa,1Takashi Kawakami,1 Masahiro Ehara,2 Mitsutaka Okumura,1Haruki Nakamura, 3 Kizashi Yamaguchi4
1
Graduate School of Science, Osaka University, Japan
2
Institute for Molecular Science, Japan
3
Protein Institute, Osaka University, Japan
4
TOYOTA Physical & Chemical Research Institute, Japan,
I. Introduction
Recently we have investigated manganese cluster in photosytem II [1], whichcatalyze the decomposition reaction of water. We rely on the newest and most reliable
X-ray structure [2] and the optimized ones starting from the X-ray structure. However
the stable spin states for some of them calculated by the B3LYP method are notconsistent with the EPR experimental results of the native cluster [1]. We are now
examining the modeling structure including various protonation types to the oxygens
in-and-around the cluster. It is also possible that the B3LYP does yield incorrectmagnetism of the manganese cluster. To confirm this, we implement of benchmark
test of B3LYP, as well as other functionals, for calculations of magnetism of various
manganese complexes [3].
II. Results
First we construct a test set consisting of 15 dinuclear manganese complexes, forwhich the X-ray diffraction and the magnetic susceptibility experiments have been
implemented. The set of complexes include various oxidation patterns: Mn(II)2
Mn(II)Mn(III), Mn(III)2, Mn(III)Mn(IV), and Mn(IV)2. Then we examine the basis set
dependence of the calculational results of magnetism of the test set with using B3LYP
functional to choose the appropriate basis set, with which the deviations of magnetic
interactions from computational results of triple-zeta plus diffuse polarization basis arealmost negligible. With employing this pruned basis set, we examined various
exchange-correlation functionals, BHandHLYP, CAM-B3LYP, TPSSh, PBE0, PBEh35,
HSEh1PBE, HSE1PBE, HSE2PBE, LC-wPBE, M06, M062-2X, M06-HF, HF, B3LYP*,
for calculations of magnetism of the test set.
The computational results will be
discussed in relation to the experimental resuls, in particular with focusing on thedependency on the oxidation states and molecular structures.
References[1] K. Kanda et al. CPL 506 (2011) 98; S. Yamanaka, et al. CPL in press; K. Kanda et al.
Polyhedron submitted; S. Yamanaka et al. Advanced in Quantum Chemistry, submitted.
[2] Y. Umena, K. Kawakami, J-R. Shen, N. Kamiya, Nature 473 (2011) 55.
[3] S. Yamanaka et al., in preparation.

266

3PP-18

Computational Investigation on Adsorption and Dissociation of NH3
Molecule on Fe(111) Surface, Hsin-Tsung Chen,1 and Yung-Chi Chen2 Hui-Lung Chen2*
1
2

Department of Chemistry, Chung Yuan Christian University, Chungli 32023, Taiwan
Department of Chemistry, Chinese Culture University, Taipei, 111, Taiwan

Abstract
Our calculations with spin-polarized density functional theory was carried out tocharacterize the adsorption and dissociation of NH3 molecule on the Fe(111) surface.
The molecular structures and adsorbate/substrate interaction energies of NH3/Fe(111),
NH2/Fe(111), NH/Fe(111), N/Fe(111) and H/Fe(111) configurations were predicted.
In these calculations, four adsorption sites, such as top (T), bridge (B), 3-fold-shallow(S) and 3-fold-deep (D) sites, of the Fe(111) surface were considered. It was shownthat the barriers for the stepwise NH3 dissociation reaction, NH3(g)Æ N(a)+3H(a), are28.32 kcal/mol (for H2N-H bond activation), 28.49 kcal/mol (for HN-H bondactivation), and 25.34 kcal/mol (for N-H bond activation), respectively, and the entire
process is 20.08 kcal/mol exothermic. To gain insights into the catalytic activity of theFe(111) surface for the dehydrogenation of NH3, the interaction nature between
adsorbate and substrate is also analyzed by the detailed electronic analysis. This
information with regard to the reaction mechanism, the catalytic activity of various
surface sites, and the relevance of the surface structure would be otherwise difficult toachieve with experimental measurements, indicating that the periodic DFT
calculations might play a significant role in the reasonable explication of NH3
dissociation behavior in heterogeneous catalysis.
Keywords: Density-functional theory; Fe(111) surface; NH3; dehydrogenation
Reference:
1. Ertl, G. Catal. Rev.-Sci. Eng. 1980, 21, 201.
2. Delbecq, F.; Zaera, F. J. Am. Chem. Soc. 2008, 130, 14924.
3. Chen, H.-L.; Chen, H.-T.; Ho, J.-J. Langmuir 2010, 26, 775.
4. Chen, H.-L.; Wu, S.-Y.; Chen, H.-T.; Chang, J.-G.; Ju, S.-P.; Tsai, C.; Hsu, L.-C.
Langmuir 2010, 26, 7157.

*Corresponding author. E-mail: chl3@faculty.pccu.edu.tw267

3PP-19

Spin-orbit TDDFT calculations with long-range correction
Ayako Nakata,1 Takao Tsuneda,2 Kimihiko Hirao3
1
Computational Materials Science Unit, National Institute for Materials Science, Japan
2
Fuel Cell Nanomaterials Center, University of Yamanashi, Japan
3
RIKEN Advanced Institute for Computational Science, Japan
Relativistic time-dependent density functional theory (TDDFT) is a powerful tool
to include both relativistic and correlation effects with low computational cost. However,
TDDFT with conventional exchange functionals have severe problems in e.g. thereproducibility of charge transfer (CT) and Rydberg excitation energies and oscillator
strengths. These problems are due to the lack of long-range exchange interactions inconventional exchange functionals. We have proposed long-range corrected (LC) DFT
and have overcome these problems. Especially, LC-TDDFT succeeds in describing CT
excitations with remarkable accuracy. CT excitations often play a major role inspin-forbidden transitions, such as phosphorescence, because the spin-orbit (SO)couplings are significant for excitations inducing the changes in electron distributions.
In this study, LC-DFT has been applied to a spin-orbit TDDFT to describe
spin-forbidden transitions appropriately by TDDFT.
The LC method has been combined with the 2-component zeroth-order regularapproximation (ZORA). In the LC scheme, the exchange energy is divided into
long-range interaction and short-range interaction parts, which are represented by the
Hartree-Fock (HF) exchange and exchange functional, respectively. The D–D, D–E, E–D,
and E–E long-range HF exchange energies have been evaluated in the SO-LC
calculations. The short-range exchange functional has been treated in the noncollinear
approach in the TDDFT calculations.
Table 1 shows the excitation energies and fine structures of a Rn atom calculatedwith LDA, BLYP, B3LYP, and LC-BLYP using the Gaussian basis function optimized in
the relativistic calculations. LC-BLYP reproduces the spin-forbidden excitation energies
for which electrons
Table 1. 6p o 7s excitation energies and fine structures of Rn [eV].
are moved to widelyStateLDA BLYP B3LYP LC-BLYP
Exptl.
distributed orbitals.
Excitation energy
Our results also
2
6.38
6.09
6.40
6.86
6.77
demonstrated that LC1
6.54
6.26
6.57
7.06
6.94
DFT accurately
0
9.69
9.31
9.73
10.47
10.66
reproduces ionization
1
9.75
9.39
9.79
10.54
10.79
energies of heavy
Fine structure
atoms based on the
2
0.00
0.00
0.00
0.00
0.00
Janak’s theorem.
1
0.16
0.17
0.17
0.19
0.17

0
1

3.31
3.37

3.22
3.29

268

3.33
3.39

3.61
3.68

3.89
4.02

3PP-20
Comprehensive study of hybrid functionals applied to structural and electronic
properties of semiconductors and insulators
Yu-ichiro Matsushita, Kazuma Nakamura, Atsushi Oshiyama
Department of Applied Physics, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
CREST, JST, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan University of Tokyo
Local density approximation (LDA) and generalized gradient approximation (GGA) in density functional theory (DFT) has
shown fantastic performance in understanding and even predicting material properties in spite of its relatively simple treatmentof the exchange-correlation functional: e.g., for many materials, lattice constants and bulk moduli are reproduced within lessthan 1-2 % and several percent, respectively, deviations from experimental values in conventional approximation. Yet theapproximations fail to describe some of the properties including ground-state magnetic ordering for some transition-metaloxides. The hybrid functionals combining LDA or GGA with the Hartree-Fock approximation (HFA) would be effective to
break limitations of LDA and GGA. Recently, a success of application of Heyde-Scuseria-Ernzerhof (HSE) functional [1] toextended systems has been reported [2], but the numbers of such calculations and applications are still quite few.
In the present study, we present a comprehensive study
about performance of several hybrid functionals,
HSE, and long-range corrected (LC) hybrid functional[4]. Our code was implemented in Tokyo Ab initio
Program Package with plane-wave-basis set andnorm-conserving

pseudopotentials.

For

structuralparameters, hybrid functionals generally give better
agreements with experiments than GGA; in HSEfunctional, the lattice constants and the elastic constants

Calculated band gap (eV)including the Perdew-Burke-Ernzerhof-free (PBE0) [3],Group I14

are well described within 1.39 % and 5.4 % accuracy,

12
10
8
6
4

functional reproduces the lattice constants within

exact
GGA

2
0

respectively, with respect to experimental values. LC

Group II

0

2

4

6

8

10 12 14

Experimental band gap (eV)1.21 % and the elastic constants within 5.5 %. Figure1

FIG.1: Comparison between theory and Expt.

compares theoretical band gaps based on GGA, HSE,
and LC with the experiments, from which, while the

GGA gaps are severely underestimated, the use of the hybrid functionals improves this underestimations [5].
References[1] J. Heyd, G. E. Scuseria, and M. Ernzerhof, J. Chem. Phys. 118, (2003) 8207.
[2] J. Paier, M. Marsman, K.Hummer, G. Kresse, I.C.Gerber, and J.G.Angyan, J. Chem. Phys. 124, (2006) 154709.
[3] J. P. Perdew, M. Ernzerhof, and K. Burke, J. Chem. Phys. 105, (1996) 9982.
[4] H. Iikura, T. Tsuneda, T. Yanai, and K. Hirao, J. Chem. Phys. 115, (2001) 3540.
[5] Y. Matsushita, K. Nakamura, and A. Oshiyama, Phys. Rev. B in press.

269

3PP-21         
     

            
          !"  #$% &#$ '( #) ##     #   *$   !  "  #$ $#  #%&#  " && #'& ()*'+, !#! # --   ')  "!  . /  0  '12  3 '   -     #$#  
&## # , # #   0#  ##! -##$  ##""!# 0 4  !'
!      -  #  !-   "  5 & !    "    %   - #%& ./, ## &## #  4  ! #! " 0 #& !6 # 7'
1 #./8  # #"! #!  &&! 
. /   9 9  9   ##$./5!  :9   9# ' ; 1 #, #1&  <==(88>*./     + 1 #1 #+ =  >(88?*

270

3PP-22

Implementation and numerical assessment oflocal response dispersion method
Yasuhiro Ikabata,1 Hiromi Nakai1,2,3
1
Graduate School of Advanced Science and Engineering, Waseda University, Japan
2
Research Institute for Science and Engineering, Waseda University, Japan
3
JST-CREST, Japan Science and Technology Agency, Japan
Various types of dispersion correction methods have been developed to improvethe description of weak interactions within the DFT framework. One of them is the local
response dispersion (LRD) method [1,2], which computes dispersion energy directlyfrom the ground-state electron density without fairly excess cost. The LRD method
combined with the long-range corrected (LC-BOP) functional improves the potential
energy curve of benzene dimer, as shown in Figure 1. This method has been integrated
to the public edition of the GAMESS program package.
In this poster, we present the theoretical aspects of the LRD method, such asenergy formulation, SCF implementation, analytical gradient, and TDDFT calculations.
We also mention the numerical assessment of the LRD method not only for theclosed-shell ground state but also for open-shell and excited states.

,QWHUDFWLRQHQHUJ\ NFDOPRO





/&%23/&%23/5'>@/&%23/5'>@/&%23/5'>@&&6' 7 &%6












5 Å



Figure 1. Potential energy curves of sandwich benzene dimer. [m,n] means thetruncations of two-center and multicenter contributions after mth and nth orders,
respectively. The aug-cc-pVTZ basis set is used in the LC-BOP+LRD calculation.
The CCSD(T)/CBS curve is taken from Ref. [3].
[1] T. Sato and H. Nakai, J. Chem. Phys., 131, 224104 (2009).
[2] T. Sato and H. Nakai, J. Chem. Phys., 133, 194101 (2010).
[3] C. D. Sherrill, T. Takatani, and E. G. Hohenstein, J. Phys. Chem. A, 113, 10146(2009).

271

3PP-23&URVVLQJEHWZHHQSRWHQWLDOHQHUJ\VXUIDFHVLQ S\ULGLQ\O 
IXUDQRO+RVVHLQ7DYDNRO'HSDUWPHQWRI&KHPLVWU\)DFXOW\RI6FLHQFH8QLYHUVLW\RI=DERO=DERO,UDQ
3RWHQWLDOHQHUJ\VXUIDFHVFDQEHDSSOLHGWRSUHVHQWLQJPROHFXODUG\QDPLFPRWLRQVVXFK DV URWDWLRQV DQG FKDQJHV LQ ERQG OHQJWKV DQG ERQG DQJOHV 6WXGLHV RI PROHFXODUG\QDPLFV KDYH EHHQ RI LQWHUHVW LQ ERWK FRPSXWDWLRQDO DQG H[SHULPHQWDO UHVHDUFKDUHDV>@5HFHQWO\G\QDPLFSKHQRPHQDVXFKDVURWDWLRQV>@DQGWDXWRPHULVP>@KDYHEHHQ
WKH VXEMHFW RI WKHRUHWLFDO UHVHDUFKHV ,Q WKLV OLQH SRWHQWLDO HQHUJ\ VXUIDFHV 3(6V  IRUG\QDPLFPRWLRQKDYHEHHQVWXGLHGE\ERWKFRPSXWDWLRQDODQGH[SHULPHQWDOPHWKRGV>@ ,Q FRQWLQXDWLRQ RI RXU SUHYLRXV UHVHDUFKHV DERXW WDXWRPHULVP>@ DQG LQ RUGHU WR
LQYHVWLJDWH WKH SRVVLELOLW\ RI GLDEDWLF FURVVLQJ LQ 3(6V RI RUJDQLF PROHFXOHV E\WKHRUHWLFDO PHWKRGV  S\ULGLQ\O IXUDQRO DQG (  S\ULGLQ + \OLGHQH 
IXUDQ + RQH KDYH EHHQ FRQVLGHUHG WR VWXG\ RI WKHLU WDXWRPHULVP LQWHUFRQYHUVLRQVUHODWLYHURWDWLRQVRIULQJV2+ERQGURWDWLRQVDQGSRVVLELOLW\RIFURVVLQJEHWZHHQWKRVHHQHUJ\ VXUIDFHV XVLQJ ')7 PHWKRGV DW WKH %/<3*  OHYHO RI WKHRU\ 7KHRSWLPL]HG VWUXFWXUHV RI ERWK WDXWRPHUV DQG WKH WUDQVLWLRQ VWDWH RI WDXWRPHULVP DUHFRPSOHWHO\ SODQDU 6WXG\ RI WDXWRPHULVP LQ 3<)2 VKRZV WKDW 7 WDXWRPHU LV DERXWN-PROPRUHVWDEOHWKDQ77KHUDWHFRQVWDQWVRIWDXWRPHULVPLQWHUFRQYHUVLRQIRU
FRQYHUWLQJ 7 WR 7 LV î 06HF DQG IRU FRQYHUWLQJ 7 WR 7 LV î
06HF DW URRP WHPSHUDWXUH WKDW VKRZ WKH SRVVLELOLW\ RI WKLV WDXWRPHULVP ZLWK KLJKUDWH DW DPELHQW WHPSHUDWXUH 5RWDWLRQ RI 2+ ERQG LQ 7 VKRZV WZR PLQLPXP DW R
JOREDOPLQLPXP DQGR ORFDOPLQLPXP DQGDWUDQVLWLRQVWDWHDWR DQGR 
ZLWKN-PROEDUULHUHQHUJ\5HODWLYHURWDWLRQRIULQJVVKRZVJOREDOPLQLPXPDWR
IRU ERWK WDXWRPHUV DQG ORFDO PLQLPXP DW R DQG R IRU 7 DQG R IRU 7 7KHEDUULHUHQHUJ\IRUULQJURWDWLRQRI7ZDVREVHUYHGDWRDQGRZLWKN-PROKHLJKWV DQG IRU 7 ZDV REVHUYHG DW  ZLWK  N-PRO KHLJKW ,QWHUHVWLQJO\ WKHHQHUJ\OHYHOVRIULQJURWDWLRQVIRU7DQG7DUHWKHVDPHDQGFURVVLQJEHWZHHQWKHP
ZDV REVHUYHG7KHUHIRUHDOWKRXJKWKHVHWZRSRWHQWLDOVKDYHQRWWKHVDPHV\PPHWULHV
EXWEHFDXVHRIWKHFURVVLQJEHWZHHQWKHLUHQHUJ\OHYHOFURVVLQJLVQRWDYRLGHG 
5HIHUHQFHV >@&:DQJ3=KDQJ-&KHP3K\V
>@6:L-6SDQR:$'XFNHU-3K\V&KHP&>@$0LVUD6'DODL7+(2&+(0  
>@**UDQXFFL*0HGGHUV$09HODVFR&KHP3K\V/HWW
>@+7DYDNRO6$UVKDGL-0RO0RGHO
>@+7DYDNRO0RO6LPXO

272

3PP-24On the external source method for
Kubo-transformed quantum correlation functions
Atsushi Horikoshi
Department of Natural Sciences, Tokyo City University, JapanThe Feynman path integral formulation of quantum mechanics represents a wellestablished route for the calculation of static properties of quantum many-bodysystems at ﬁnite temperature. However, it is computationally expensive to calculate
dynamical quantities such as Kubo-transformed quantum correlation functions
 βdλK
CBA (t) =B̂(−ih̄λ)Â(t)β .
0 β
KRecently a new quantum dynamics method to calculate CBA(t) has been proposed by Krishna and Voth [1]. This is an extended quantum dynamics perturbed
by external sources [2]. In case that both of Â and B̂ depend on the position operator q̂, the calculation procedure is summarized as follows: (1) Introduce an operatordF̂ . (2) Introduce two external sources μ and ν which couple
F̂ which satisﬁes Â = dq

to the operators B̂ and F̂ , respectively. (3) Calculate the expectation value of the
momentum operator p̂, pμν (t) = ρ̂μ p̂ν (t), where the density operator ρ̂μ is givenby the Hamiltonian Ĥ + μB̂, and the time evolution of p̂ is driven by the Hamiltonian Ĥ + ν Â. (4) Diﬀerentiate pμν (t) with respect to μ, ν, and t. We obtain the
Kubo-transformed quantum correlation function using the approximate equation



∂3

+ B̂β Âβ .
pμν (t)
β ∂μ∂ν∂t
μ,ν=0

1
K
(t) 
CBA

This method is quite promising, because the path integral calculation of pμν (t)K
is expected to be less computationally demanding than that of CBA(t). It is still
unclear, however, whether the method can be applied to general quantum systems,
because the method is based on the approximate equation.
In this work [3] we derive an exact identity



∂3

K
+ B̂β Âβ + CBD(t) − B̂β D̂(t)β ,pμν (t)
β ∂μ∂ν∂t
μ,ν=0

1
K
(t) =
CBA



where D̂(t) = − h̄i 0t dsF̂ (s), ∂∂qV̂ (t) . Omitting the operator D̂(t), we obtain theapproximate equation given by Krishna and Voth. This approximation is valid in
the short time region. We will present some results for model potential systems andclarify the properties of pμν (t) and D̂(t).
[1] V. Krishna and G. A. Voth, J. Phys. Chem. B110, 18953 (2006).
[2] H. Kleinert, Path Integrals in Quantum Mechanics, Statistics, Polymer Physics,and Financial Markets, World Scientiﬁc, Singapore, 2004.
[3] A. Horikoshi, in preparation.

273

3PP-25

Zero-dipole summation method for precisely estimating electrostaticinteraction in molecular dynamics
Ikuo Fukuda,1 Narutoshi Kamiya,2 Haruki Nakamura2
1
Computational Science Research Program, RIKEN, Japan
2
Institute for Protein Research, Osaka University, JapanFor computational studies of materials in a realistic manner, even in a classicalpoint charge system, the appropriate treatment of the Coulombic interaction is important.
However, due to its long-ranged nature and the existence of both positive and negative
signatures of the potential function, it is difficult to handle the interaction in an effective
manner, i.e., with high accuracy, low computational cost, freedom from artifacts, andease of implementation.
We present a novel idea, zero-dipole summation, for evaluating the electrostatic
energy of a classical particle system, and provide an algorithm for effectively utilizing
the idea for molecular dynamics study [1]. The summation conceptually prevents thenonzero-charge and nonzero-dipole states artificially generated by a simple cutoff
truncation. The resulting energy formula is nevertheless represented by a simple
pairwise sum using a certain function, which enables effective application tohigh-performance computation with good scalability. We discuss heuristic derivation of
the energy formula for an introductory understanding, explain a theoretical framework
to justify the formula for a consistent description, and exhibit the numerical results, incomparison with the previously proposed scheme [2]. Accuracy of the energy function
and the stability in MD simulation are investigated in crystal and liquid systems. In
addition, we discuss the issue of treating bonding interactions for general molecule
system, and provide the results of the application to the systems, including bulk water.
Our method is an extension of the charge neutralized summation developed by Wolfet al [3]. Furthermore, we found that the current method becomes a generalization of the
pre-averaged potential method [4], which has been developed to tackle the artifact
caused by the cubic symmetry in the periodicity assumption, e.g., used in latticemethods, applied to inherently non-periodic systems. Note that the pre-averaged
potential method is based on a viewpoint of the isotropic property, which is different
from the viewpoint of the electric neutrality in the current method. We discuss therelationships among these methods and the possibilities for their further applications.
[1] I. Fukuda et al., J. Chem. Phys. 134, 164107 (2011).
[2] I. Fukuda, Y. Yonezawa, and H. Nakamura, J. Phys. Soc. Jpn. 77, 114301 (2008).
[3] D. Wolf, P. Keblinski, S. R. Phillpot, and J. Eggebrecht, J. Chem. Phys. 110, 8254
(1999).
[4] E. Yakub and C. Ronchi, J. Chem. Phys. 119, 11556 (2003).

274

3PP-26

Ab initio molecular dynamics approachto tunneling splitting in polyatomic molecules
Yusuke Ootani,1 Tetsuya Taketsugu2
1
RIKEN Advanced Institute for Computational Science
2
Division of Chemistry, Graduate School of Science, Hokkaido University, Japan

Nowadays, ab initio molecular dynamics (AIMD) has been widely used toinvestigate dynamical process of chemical reaction. AIMD does not require apredetermined potential function, and thus it can be applied to any polyatomic moleculein principle. In the AIMD approach, nuclear motions are evolved by integrating the
Newton's equation of motion based on the energy gradient calculated point by point by
ab initio methods. Thus, nuclear motion is treated by classical mechanics, and so some
additional treatment is required to take into account nuclear quantum effects such as
nonadiabatic transition and tunneling effects.
Recently, AIMD has been extended to excited-state reaction dynamics in which
nonadiabatic transition plays an important role. Several approaches such as a surface
hopping method, are successfully used to incorporate the nonadiabatic transition in aframework of classical trajectory simulation. On the other hand, there are few ways totackle the tunneling effect and there have been no attempt to implement a semiclassicaltunneling method to AIMD simulations.
In this work the semiclassical tunneling method of Makri and Miller [1] is
implemented to our developed AIMD code as apractical tool to investigate the tunneling Table 1. Calculated tunneling
effects in chemical reactions. Each time the splitting and experimental value
turning point for tunneling is detected along the (in cm-1)
AIMD trajectory, the tunneling amplitude isCal.
Exp.[2]
evaluated on-the-fly through ab initio electronic
NH3
0.71
0.79
structure calculation. The method is applied to
ND3
0.078 0.053
umbrellainversionofammoniaand
HOCH=CH-CHO 19.8
21.6
intramolecularhydrogentransfer
in
DOCH=CH-CHO 2.28
2.9malonaldehyde. In the application tomalonaldehyde, effects of multi-dimensionality are examined by assigning quantum
zero-point energies only to significant vibrational modes and changing the amount ofenergy given to other degrees of freedom. The calculated tunneling splitting values arein good agreement with the corresponding experimental values for both molecules, as
shown in Table 1.
[1] N. Makri and W. H. Miller J. Chem. Phys. 91, 4026 (1989).
[2] V. Spirko, J. Mol. Spectrosc. 101, 30 (1983): S. L. Baughcum et al. J. Am. Chem.
Soc. 106, 2260 (1984).

275

3PP-27

Short-time Fourier transform analysis of electron dynamics
described by real-time TDHF calculation
Tomoko Akama,1 Akihiro Hiratsuka,1 Yutaka Imamura,1 Hiromi Nakai1,2,3
1School of Advanced Science and Engineering, Waseda University, Japan
2
Research Institute for Science and Engineering, Waseda University, Japan
3
CREST, Japan Science and Technology Agency, Japan
I. Introduction
The real-time time-dependent Hartree-Fock and time-dependent density functional
theory (RT-TDHF/TDDFT) calculations have become useful tools not only forevaluating excitation spectra but also for describing electron dynamics. In preceding
RT-TDHF/TDDFT studies, the frequency-domain properties were obtained by the
Fourier transform technique and the electron dynamics was analyzed directly throughtime evolutions of molecular properties. In this study, we proposed an analysis of
RT-TDHF calculations using the short-time Fourier transform (STFT) technique.
II. Short-time Fourier transform analysis of RT-TDHF calculation
In the RT-TDHF calculation, the TDHF equation is solved by the real-time
propagation method to obtain the time-dependent induced polarization vector. STFT is atime-frequency analysis technique, transforming a time-domain property into afrequency-domain one with leaving time-domain information. The STFT analysis isapplied to the induced polarization vector,

GP (Z , t )f³ dW GP (W )W (W  t ) e

 iZW

f

,

(1)

IntensityIm[G Py(Z ,t)]Im[G Pz(Z ,t)]where W (t ) is a window function that picks up a part of the signal in the time domain.
Time evolution of excitation spectra is obtained as Im>GP (Z , t )@ .
We carried out RT-TDHF/cc-pVDZ calculation and STFT analysis of formaldehyde
dimer, in which two molecules, Į and ȕ, are vertically arranged. Figure shows the time= 9.9 eVevolution of the excitation peaks at 9.9 eV, mainlyhZassigned
to the ʌ-ʌ* excitations of
the molecules Į and ȕ. The intensities of thesemolecule ȕpeaks oscillate. The phase of the oscillation of㪇
molecule ȕ differed by about ʌ/2 from that ofmolecule Į. This shows that the induced
polarization propagates from the ʌ-ʌ*molecule Į
excitation of the molecule Į to that of ȕ,㪇through the intermolecular interaction. The
STFT analysis of RT-TDHF calculation
enables us to directly observe the electron
0
10
20
30
40
50
60
70
dynamics associated with the excited states.
Time t [fs][1] T. Akama and H. Nakai, J. Chem. Phys. 132,054144 (2010).

276

Fig. Time evolution of peak intensities
corresponding to ʌ-ʌ* excitations ofmolecules Į and ȕ.

3PP-28

Computational study on photo- and thermo-reactions between
tetra-tert-butyl-substituted cyclobutadiene and tetrahedrane
Masato Sumita,1 Kazuya Saito,2 Yoshitaka Tateyama1
1
WPI International Centre for Materials Nanoarchitectonics (MANA), National Institutefor Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan2
Department of Chemistry, Graduate School of Pure and Applied Sciences,
University of Tsukuba, 1-1-1, Tennodai, Tsukuba, Ibaraki 305-8571, JapanWe
haveinvestigatedthephoto-chemical
reactionfromtetra-tert-butylcyclobutadiene (TB-CBD) to tetra-tert-butyltetrahedrane (TB-THD) and
its reverse thermo-chemical reaction processes in the ground state [1] by using CASSCF
and MRMP2 computational methods. The initial step of the photochemical reaction is
the HOMO-LUMO single-electron excitation (11B1 state) and the rearrangement from
TB-CBD to TB-THD occurs via the HOMO-LUMO double electron excited state (21A1
state). After the transition from the 11B1 to the 21A1 state, most TB-CBD molecules
only show photo-physical property without any reactions because the final point of theminimum-energy-path (MEP) calculation at the MRMP2//CASSCF level is the S1/S0
degeneracy space (DSionic), which results in turning back to TB-CBD in the S0 state.
However, on the way to the final point of the MEP, it is possible for some TB-CBD totransit at another S1/S0 degeneracy space (DStetra), which is related to the photoreaction
from TB-CBD to TB-THD. The processes of the photoreaction from TB-DBD to
TB-THD are schematicallysummarized in Figure 1. On
the other hand, two routes
from TB-THD to TB-CBD
were found in the S0 state.
One is the route via
bicycldiradicaltransition
state. The other is the ionictransition state. In bothreaction paths, only one TS
is there in contrast to the Figure 1. Schematic potential energy surfaces. TB-CBD
pluralstep
reaction isomerizes to TB-THD via the HOMO/LUMO double-electron
excited state via the HOMO/LUMO single-electron excitedsuggested previously [2].
state.

[1] G. Maier, Angew. Chem. Int. Ed. Engl. 27 (1988) 309.
[2] M. Sumita. K. Saito. Tetrahedron, 66 (2010) 5212.

277

3PP-29

Photophysical properties and vibrational structure of ladder-typepenta p-phenylene and carbazole derivatives based on SAC-CI
calculations
Potjaman Poolmee,1 Masahiro Ehara,2 Hiroshi Nakatsuji3
1
Department of Chemistry, Faculty of Liberal Arts and Science, Kasetsart University,
Kamphaeng Saen, Nakhon Pathom, Thailand
2
Research Center of Computational Science, Institute for Molecular Science,
38-Nishigo-Naka, Myodaiji, Okazaki, Japan
3
Quantum Chemistry Research Institute, Goryo Oohara 1-36, Nishikyo-ku, Kyoto, JapanThe ʌ-conjugated ladder-type molecules constitute an attractive field of organic photoactive
materials. In this work, the photophysical properties of ladder-type penta p-phenylene (LPP) andcarbazole derivatives (bisindenocarbazole and diindolocarbazole) have been theoreticallyinvestigated by using the symmetry-adapted cluster-configuration interaction (SAC-CI) method.
The equilibrium geometries in the ground (S0) and first excited (S1) states were calculated to beplanar and the excitation is delocalized over the molecules. The SAC-CI/DZP calculations havebeen applied to the absorption and emission spectra of these molecules. The absorption spectra
were well reproduced in both peak positions and the shape of the absorption bands. The strong
absorption is attributed to the HOMOĺLUMO (HĺL) transition, however, in carbazoles, theH-1ĺL transition is located below the HĺL transition. The vibrational structure in the S0-S1
absorption band of LPP was analyzed by calculating the Franck-Condon (FC) factors based on
the potential energy surfaces (PESs) along the normal coordinates that are relevant in thegeometry change. The vibrational structure was well reproduced by the theoretical simulation.
The C-C stretching mode dominantly contributes to the vibrational structure, while thebreathing motion of molecular frame does not influence the structure. The emission energies
calculated by the SAC-CI method also agree well with the experimental values. The vibrational
structure in the fluorescence band was also examined by the FC analysis, for which theoretical
spectrum is satisfactory for two carbazoles, while the 0-0 transition is overestimated in LPP. In
diindolocarbazole, the S2 state has large oscillator strength, while the S1 state has small oscillator
strength.

278

3PP-30

Probing the multiradical character and nonlinear optical properties oflinear and cyclic polyacenes: a wrapping effect in open-shellpolyacenes
Shabbir Muhammad, Takuya Minami, Ryohei Kishi, Yasuteru Shigeta,
Masayoshi Nakano
Department of Materials Engineering Science, Graduate School of Engineering
Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
I. Introduction
We have applied the broken-symmetry density functional theory method to theinvestigation of the second hyperpolarizabilities (γ) and multiradical characters (yi) [1]of zigzag (Z) linear and cyclic polyacenes [2].

It has been found that linear [n]acenes

when wrapped into their respective [n]cyclacenes show a significant change in theirsinglet diradical characters.

For example, [5]acene by wrapping into [5]cyclacenechanges its only primary diradical value of y0 = 0.407 into two identical values ofdiradical characters, y0 = y1 = 0.487 for [5]cyclacenes.

In contrast, wrapping of[6]acene into [6]cyclacene increases its primary diradical value from y0 = 0.540 to y0 =0.844 with further emergence of two smaller identical values y1 = y2 = 0.156. These
results show interesting insights into the relationship among the architectures, diradical
characters and γzzzz values. Besides this, more pronounced but different effects on theseproperties have been observed by comparing zigzag graphenes to their respective
wrapped nanotubes.
Table 1. Diradical characters (y0, y1) and γzzzz values for zigzag polyacenes
Systemsy0

y1

γzzzz (a.u.)

Z-(5)acene

0.40780.06296.01E+03

Z-(6)acene

0.54090.1162

6.37E+03

Z-(7)acene

0.64410.1773

6.41E+03

Z-(8)acene

0.72560.2465

6.47E+03

Z-(9)acene

0.79410.3194

6.62E+03

Z-(10)acene

0.84550.3914

6.93E+03

Z-(5)cyclacene

0.48700.48702.89E+03

Z-(6)cyclacene

0.84470.1561

1.80E+03

Z-(7)cyclacene

0.66180.6618

2.83E+03

Z-(8)cyclacene

0.85080.2574

2.53E+03

Z-(9)cyclacene

0.80740.8074

3.00E+03

Z-(10)cyclacene

0.85190.38803.36E+03

279

Figure1. Wrapping and unwrapping patternsof polyacenes
References[1] M. Nakano et al., Phys. Rev. Lett. 99,
033001 (2007).

[2] Anthony, J.E. Angew. Chem. Int. Ed.
2008, 47, 452-483

3PP-31

Reactivity of thiophenolate toward chalcogenadiazoles
N.P. Gritsan1, E.A. Suturina1, A.V. Zibarev2
1

Institute of Chemical Kinetics and Combustion of RAS, Institutskaya str. 3,
Novosibirsk, 630090, Russia

2

Institute of Organic Chemistry of RAS, Lavrentieva ave. 9, Novosibirsk, 630090, Russia

Thiophenolate anion (1) is known to reduce a series of chalcogenadiazoles to radical
anions (π-RAs) [1]. Recently [2], it was discovered that reaction of 1 with
3,4-dicyano-1,2,5-selenadiazole (2) gives the product of hypercoordination at the Se
center (3) isolated in the form of the salt [K(18-crown-6)][3] (4). The latter type ofreactivity has never been observed previously. The X-ray structure of 4 revealed that the
Se-S distance in the anion 3 (2.722 Å) is ca. 0.5 Å longer than the sum of the covalentradii, but ca. 1 Å shorter than the sum of van der Waals radii of Se and S [2].
NC
S

Se

+

1

NC

N

NC

2

N

NC

N
Se
N

S

3

To estimate the scope of this new reaction, thermodynamics and kinetics of theinteraction between 1 and various 1,2,5-chalcogenadiazoles (chalcogen: S, Se, Te) weretheoretically investigated at the DFT level using B3LYP, M06-2X and B97-D
functionals. Calculations predict that hypercoordination of 1 with formation of the S-Sbond is almost thermoneutral. The hypercoordinate products with the Se-S bond arethermodynamically more preferable. In turn, interaction of 1 with Te congener of 2 ispredicted to lead to hypercoordinate anion featuring stronger Te-S bond than the Se-S
bond in anion 3. Therefore, one can expect general character of the discussed
hypercoordination in the case of heavier chalcogens. According to the QTAIM and NBO
analysis, the Se-S bond in 3 is a donor-acceptor bond whose formation leads to transfer ofca. 40% of negative charge from 1 onto the heterocycle.
For various 1 / chalcogenadiazole reaction systems, thermodynamics and kinetics ofelectron transfer reaction were also theoretically studied to rationalize interchalcogenhypercoordination vs. reduction to π-RA dichotomy.
ACKNOWLEDGEMENTS. The authors are grateful to the RFBR (project 10-03-00735)
and the Russian Ministry of Education and Science (project No. 14.740.11.0716) for
financial support.
[1] I.Yu. Bagryanskaya, Yu.V. Gatilov et al. Eur. J. Inorg. Chem. 2007, 4751.
[2] N.A. Semenov, E.A. Suturina et al. J. Phys. Chem. A 2011, DOI: 10.1021/jp2019523.

280

3PP-32

Molecular and Electronic Structures of the Super Reduced State of a
Polyoxometalate (POM), [Mo12O40P]x (x = -3, -27)
Yoshio Nishimoto,1 Hirofumi Yoshikawa,1 Kunio Awaga,1 Stephan Irle1
1
Graduate School of Science, Department of Chemistry, Nagoya University, Japan
Polyoxometalate (POM) clusters have a great potential as novel battery material
with higher electronic capacity and stability. Its useful electrochemical properties inthis regard were spectacularly demonstrated by Kawasaki et al. [1], and its stability
under solid-state electrochemical redox conditions is of great importance for practicalapplication. Its wide range of charge states is of great interest to theoretical chemists.
In our contribution, the molecular and electronic structures of a POM cluster,[Mo12O40P]x (x = 3-, 27-), were investigated using density functional theory (DFT). In
the super-reduced state, which is achieved by reduction of POM3- by formally 24
electrons, experimentalists found in the XAFS spectrum that the POM27- cluster has
characteristic short (about 2.5 Å) Mo-Mo bonds and suffers characteristic geometricalchanges of Mo-O bond lengths [2]. This observation was practically reproduced by ourtheoretical calculations at the RI-BP86-D/def-SVP level of theory, using lithium atoms
as counter cations in order to stabilize the highly negative charge on the POM cluster.
It was proven that the origin of observed short Mo-Mo bonds comes from the formationof triangular Mo-Mo sites, created under preservation of the original Mo skeleton via‘squeezing out’ oxygen atoms from Mo-O-Mo bonds.
We note that our calculations were not only performed using ordinary geometry
optimizations, but also employed the Born-Oppenheimer molecular dynamics (BOMD)
technique. Starting with the structure of X-ray result, we first added 27 Li atoms in
random positions. In Figure 1, the lower left structure was derived by an ordinary
geometry optimization; on the other hand, the upper right structure was derived by
quenching a BOMD NVT trajectory run at room temperature for 1.92 ps. Its resulting
optimized geometry fits the experimental XAFS observations better, and is lower inenergy by about 3 eV than the straightforwardly optimized geometry.
Finally, another important character of the POM
cluster, the reverse process (POM27- Æ POM3-), wasalso verified. On depriving 24 electrons via removalof the 27 Li atoms from the super-reduced state, it was
confirmed that the molecular structure was reverted to thegeometry of the 3- state in a straightforward geometry
optimization.
[1] N. Kawasaki et al. Angew. Chem. 2011, 123, 3533.
[2] H. Wang, H. Yoshikawa, K. Awaga et al., in
preparation.
Figure 1. Optimized Structuresof POM27-.

281

3PP-33

Electronic structure of transition metal systems
from X-ray spectroscopy
Marcus Lundberg,1,2 Serena DeBeer,3 Uwe Bergmann,4 Samuel Wilson,2 Britt
Hedman,4 Keith O. Hodgson,2,4 Edward I. Solomon2,4
1
Department of Physical and Analytical Chemistry, Uppsala University, Sweden
2
Department of Chemistry, Stanford University, USA
3
Department of Chemistry and Chemical Biology, Cornell University, USA
4
SLAC National Accelerator Laboratory, USA
X-ray spectroscopy is a powerful probe of the electronic and geometric structure oftransition metal enzymes and catalysts. A shortcoming of most methods is that the short
lifetime of the core hole leads to a broadening that is larger than the energy difference
between the electronic states of interest. This limitation can be overcome by scattering
techniques, i.e., resonant inelastic X-ray scattering. In these experiments the energy
transfer between the X-ray photon and the sample replaces the absorption energy in
X-ray absorption spectroscopy (XAS) as a probe of the different energy levels. The
improved energy resolution is due to the fact that the experiment does not directly
observe a state with a deep core hole. We have experimentally studied scattering of hard
X-rays, corresponding to a 2p  3d excitation (metal L-edge), to investigate
metal-ligand bonding in iron model complexes and enzymes. As a first stage, we haveinterpreted the spectra using a parameterized valence bond configuration interaction(VBCI) model based on atomic multiplets, and show how the spectral information canbe used to probe chemical bonding.

Figure 1. a) 1s2p RIXS plane of ferrocyanide. b) Experimental L-edge XAS spectrum
compared to “L-edge-like” RIXS cut. c) VBCI multiplet simulations of L-edge and
RIXS cut.

282

3PP-34$WKHRUHWLFDOVWXG\RQSURWRQFRQGXFWLRQLQQLWURJHQGRSHG6U7L2
SHURYVNLWH

7DNX2QLVKL 7U\JYH+HOJDNHU'HSDUWPHQWRI&KHPLVWU\IRU0DWHULDOV*UDGXDWH6FKRRORI(QJLQHULQJ
0LH8QLYHUVLW\-DSDQ
7KH&HQWUHRI8OWLPDWH7HFKQRORJ\RQ1DQR(OHFWURQLFV0LH8QLYHULVW\-DSDQ
7KH&HQWUHIRU7KHRUHWLFDODQG&RPSXWDWLRQDO&KHPLVWU\ &7&& 'HSDUWPHQWRI
&KHPLVWU\8QLYHUVLW\RI2VOR1RUZD\,,QWURGXFWLRQ
3URWRQFRQGXFWLYH PDWHULDOV KDYH UHFHQWO\ DWWUDFWHG PXFK LQWHUHVW GULYHQ E\ WKHVHDUFKIRUHIILFLHQWSURWRQLFHOHFWURO\WHVLQVROLGR[LGHIXHOFHOOV 62)&V   $VLVZHOONQRZQ 6U7L2 SHURYVNLWH RI FXELF VWUXFWXUH VKRZV SURWRQ FRQGXFWLYLW\ DW KLJKWHPSHUDWXUHV  7RHQKDQFHSURWRQFRQGXFWLYLW\)HDQG $OGRSLQJ DWWLWDQLXPVLWHKDV
EHHQH[SORUHG  ,QSDUWLFXODUYHU\UHFHQWO\1RUE\HWDOLQYHVWLJDWHGQLWURJHQGRSLQJLQ
WKH SURWRQ FRQGXFWLYH =U2  ,Q WKLV VWXG\ K\EULG')7 FDOFXODWLRQV KDYH EHHQSHUIRUPHG WR H[DPLQHQLWURJHQGRSLQJDWWKHR[\JHQVLWHDVDQDOWHUQDWLYHWR$ODQG)HGRSLQJDWWLWDQLXPVLWH,,5HVXOWDQGGLVFXVVLRQ)LJXUH  VKRZV WKH FDOFXODWHG
SRWHQWLDO HQHUJ\ FXUYH LQ WKH
6U7L21+PRGHO ZLWKORFDOPLQLPDDURXQG R[\JHQ DQG QLWURJHQ ORZHVWDURXQG QLWURJHQ  7KH DFWLYDWLRQHQHUJ\ IURP R[\JHQ WR QLWURJHQ LV
H9 ZKLOH WKH UHYHUVH EDUULHU LV
H9VLPLODUWRWKHXQGRSHGEDUULHUH9  0XFK K\GURJHQ FDQFRQVHTXHQWO\H[LVWDVSDUWRIWKH1+
LRQ WKHUHE\ HQKDQFLQJ SURWRQFRQGXFWLYLW\E\QLWURJHQGRSLQJ            )LJXUH7KHFDOFXODWHGSRWHQWLDOHQHUJ\              
FXUYHLQWKH6U7L21+PRGHO>@72QLVKL7+HOJDNHU,QW-4XDQW&KHPLQSUHVV>@-03ROIXV71RUE\5+DXJVUXG'DOWRQ7UDQVDFWLRQV



283

3PP-35

Application of the density matrix theory to the control of electronic
ring current coupled to molecular vibrations in chiral molecule
Hirobumi Mineo1, , M. Kanno2, H. Kono2, Y. Teranishi3, M. Yamaki4, S.D. Chao1, S.H.
Lin4,5 and Y. Fujimura2,51
Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan
2

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai
980-8578, Japan3

Department of Physics, National Chiao Tung University, Hsinchu 300, Taiwan

4

Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan

5Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300,
TaiwanIn recent years quantum control of moelcular and nano or mesoscopic systems has
been the subject of wide interest [1-5] for realization of the construction and design ofquantum device applications in material science. Laser control of molecular ringsystems has attracted a special attentions [6-8].
In this work we demonstrate how the linearly polarized laser pulse induces theelectronic ring currents in a chiral molecule by the use of the density matrix method.
The direction of the electronic ring currents are controlled by the polarization of thelaser pulse through pumping to the quasi-degenerate two excited states. In the present
study we consider the bi-phenol molecule which consists of the two phenols connectedby a single chemical bond, and both phenols form a distorted angle.
[1] M. Nest, F. Remacle, and R.D. Levine, New J. Phys. 10, 025019 (2008).
[2] K. P. Singh et al., Phys. Rev. Lett. 104, 023001 (2010).
[3] A. Bandruk, S. Chelkowski, and H.S. Nguyen, Int. J. Quantum Chem. 100, 834(2004).
[4] P. Krause, T. Klamroth, and P. Saalfrank, J. Chem. Phys. 123, 074105 (2005).
[5] T. Ihn et al, Europhysics News 36, 78 (2005).
[6] I. Barth, J. Manz, Y. Shigeta, and K. Yagi, J. Am. Chem. Soc. 128, 7043 (2006).
[7] I. Barth and J. Manz, Angew. Chem. Int. Ed., 45, 2962 (2006).
[8] M. Kanno, H. Kono, Y. Fujimura, and S.H. Lin, Phys. Rev. Lett. 104, 108302(2010).

E-mail: mineo@gate.sinica.edu.tw284

3PP-36

Inverse heavy-atom eﬀect in conjugated carbenes, silylenes, aldehydes
and ketones
Mojmı́r Kývala, Jakub ChalupskýInstitute of Organic Chemistry and Biochemistry, Czech Republic
I. Introduction
It is well known that the presence of an atom of high atomic number (Z), which
is either part of, or external to, a molecule can signiﬁcantly enhance the probabilityof spin-forbidden transitions between electronic states of the molecule. As thesetransitions, e.g. phosphorescence or intersystem crossing, involve electronic statesof diﬀerent spin multiplicities, the enhancement, for which the name “heavy-atom
eﬀect” came into use, may easily be attributed to the increase in spin-orbit coupling(SOC) between the states [1].
However, in a few cases an opposite, so-called inverse heavy-atom eﬀect, was observed or calculated. It was rationalized in terms of a decomposition of the Cartesian
vector of SOC between two nonrelativistic electronic states of a molecule into a sumof contributions of atoms or pairs of localized orbitals. While the length of a contribution is supposed to be always normal (complying with the empirical Z 2 rule),
its direction and orientation may be essentially arbitrary.
II. Results
We adopted the suggested explication and incorporated it in the model of 2
electrons in the 2 nearly nonbonding molecular orbitals of a biradical, as well as tothe model of 4 electrons in the 3 frontier molecular orbitals (π, n and π ∗ ) of the
carbonyl group. Combining apparent physical arguments with our computational
experience, we devised a set of simple orbital-based rules with the aid of which
the sense (positive or negative) and to a limited extent also the size of the heavyatom eﬀect on SOC between the 2 lowest closed-shell singlets S0 , S2 and the lowest
triplet T1 of planar conjugated carbenes and silylenes as well as between the 3 lowest
singlets S0 , 1 (n, π ∗ ), 1 (π, π ∗ ) and the 2 lowest triplets 3 (n, π ∗ ), 3 (π, π ∗ ) of planar
conjugated aldehydes and ketones (or N-heterocycles) can smoothly be predicted.
The reliability of the predictions is veriﬁed through quasirelativistic ab initio
calculations of the vectors of SOC between S0 (S2 ) and T1 in many carbenes andsilylenes, and among S0 , 1 (n, π ∗ ), 1 (π, π ∗ ), 3 (n, π ∗ ) and 3 (π, π ∗ ) in many aldehydes
and ketones (and several pyridines), using the full DKH1 spin–orbit Hamiltonianand state speciﬁc DKH2 CASSCF or MRCIS wave functions. For a few selected
molecules (preferably those which should exhibit strong inverse heavy-atom eﬀect)
observable properties like zero-ﬁeld splitting, integrated intensity of singlet–triplet
absorption or phosphorescence radiative lifetime are also calculated using doublegroup (spin–orbit and spin–spin) MRCIS or quasidegenerate perturbation theory.
[1] A. D. McNaught, A. Wilkinson, eds., IUPAC. Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”), Blackwell Scientiﬁc Publications, Oxford, 1997285

3PP-37

Analysis of the effect of intermolecular interactions on dielectric
properties in hydrogen-bonded material
5-bromo-9-hydroxyphenalenone
Hiroki Otaki,1 Koji Ando1
1
Department of Chemistry, Graduate School of Science, Kyoto University, Japan
It is well known that many of the hydrogen-bonded materials undergo phase transitions associated with proton (deuteron) ordering. 5-Bromo-9-hydroxyphenalenone (BrHPLN), which belongs to the zero-dimensional hydrogen-bonded system, exhibits paraelectric (PE) − antiferroelectric (AFE) phase transition in the deuterated compound [1].
However, a preliminary calculation of an isolated monomer has shown that the magnitude of molecular electronic dipole moment is too small to reproduce the experimental
transition temperature (∼ 40 K).
We here focus on the effect of intermolecular interactions on the dielectric properties
of BrHPLN. By means of density functional theory (DFT) with plane-wave basis sets andthe Fragment Molecular Orbital (FMO) methods, we have found that C−H· · ·O type intermolecular hydrogen bonding and π-π stacking interactions affect the molecular dipole
moment significantly. We also propose a Monte Carlo method with the correction of theinduced dipole moment, reflecting the results of the FMO calculation at all possible nearest neighbor trimer configurations. We shall show that the Monte Carlo simulation withthe correction results in better agreement with the experiments [2].
Acknowledgement

This research was supported by the Global COE Program “International Center for
Integrated Research and Advanced Education in Materials Science” (No. B-024) of the
Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan.
DE

Figure 1: Schematic (a) molecular and (b)crystal structure of BrHPLN.

Figure 2: Dielectric constant calculated
by Monte Carlo simulation with/without
the correction of the dipole moment.

[1] T. Mochida, A. Izuoka, T. Sugawara, Y. Moritomo and Y. Tokura, J. Chem. Phys.,101, 7971 (1994).
[2] H. Otaki and K. Ando, Phys. Chem. Chem. Phys., 13, 10719 (2011).

286

3PP-38

Electronic states of GdF assigned in jj-coupling scheme
Shigeyoshi Yamamoto,1 Hiroshi Tatewaki 2
1
School of International Liberal Studies, Chukyo University, 101-2 Yagoto-Honmachi,
Showa-ku, Nagoya 466-8666, Japan
2
Graduate School of Natural Sciences, Nagoya City University, Aichi 467-8501, Japan
I. Introduction
The electronic states of the GdF molecule [1] have been investigated with the
4-component relativistic configuration interaction (CI) method. The wave functions
are represented in the jj-coupling scheme. However, LS-coupling scheme is popularand the notation of electronic state is standardized. For example, the GdF ground stateis written as 76-7/2. The configuration of the Gd part in GdF is written as (4f)7 (6s)2.
However for molecules containing heavy elements such as lanthanides, jj-coupling
scheme is dominant. Besides the jj-coupling scheme is usually adopted in the
4-component relativistic theory. We have assigned all the electronic states of GdF
below 3.0 eV. For this assignment, we have proposed a terminology [2] for families orstates based on the jj-coupling scheme.
II. Excited states assigned with f-shell Omega decomposition method
The wave functions are classified by the projection (:) of the total angularmomentum onto the molecular axis. A series of states which start from the highest :and decrease one by one until 0 or 1/2 can be found. We called it family. We call thehighest : state root. The family members can be considered to be derived from theroot.
There are c.a. 100 states below 3.0 eV for GdF. These states have been classified
into families by the excitation energy and the f-shell Omega components weight which
is defined as follows.

weight (: f )

2
i

¦C

(1)

i: f

Here, :f denotes the angular momentum generated from the seven electrons of the (4f)molecular spinors, and Ci is a CI coefficient of the i-th Slater determinant. The
multiconfigurational CI wave function can be represented compactly with the f-shell
Omega weights.
[1] S. Yamamoto and H. Tatewaki, J. Chem. Phys. 129, 244505 (2008).
[2] S. Yamamoto and H. Tatewaki, J. Chem. Phys. 134, 164310 (2011).

287

3PP-39

105VKLHOGLQJVRIDQH[FLPHU
0LFKLNR$WVXPL   'DQLHO5RFD6DQMXiQ  +DQV-¡UJHQ$DJDDUG-HQVHQ 
7U\JYH+HOJDNHUDQG5RODQG/LQGK'HSDUWPHQWRI3K\VLFDODQG$QDO\WLFDO&KHPLVWU\4XDQWXP&KHPLVWU\ 
8SSVDOD8QLYHUVLW\6ZHGHQ'HSDUWPHQWRI3K\VLFVDQG&KHPLVWU\8QLYHUVLW\RI6RXWKHUQ'HQPDUN'HQPDUN
&HQWUHIRU7KHRUHWLFDODQG&RPSXWDWLRQDO&KHPLVWU\'HSDUWPHQWRI&KHPLVWU\ 
8QLYHUVLW\RI2VOR1RUZD\ 0XOWLFRQILJXUDWLRQDO VHOIFRQVLVWHQW ILHOG 0&6&)  PHWKRGV KDYH EHHQ XVHG WRVWXG\WKHQXFOHDUVKLHOGLQJVDWWKHORZHVWH[FLWHGVLQJOHWVWDWHRIQXFOHREDVHH[FLPHUVH[FLWHGGLPHUV 7KHRSWLPL]HGVWUXFWXUHRIH[FLPHUVZHUHUHSRUWHGE\5RFD6DQMXiQHW
DO>@ E\ FRPSOHWH DFWLYH VSDFH VHOIFRQVLVWHQW ILHOG &$66&) FRPSOHWH DFWLYH VSDFH
SOXVVHFRQGRUGHUSHUWXUEDWLRQWKHRU\ &$637 OHYHORIWKHRU\
6LQFHWKHUHDUHQRH[SHULPHQWDOUHVXOWVRIQXFOHDUFRQVWDQWVLQH[FLWHGVWDWHH[FLPHUWKH SULPDU\ FDOFXODWLRQ KDV EHHQ FDUULHG RXW IRU WKH QXFOHDU VKLHOGLQJV RI XUDFLO DW
JURXQG VWDWH  8VLQJ WKH VDPH PHWKRG H[FLPHU UHVXOWV IRU WKH JURXQG VWDWH DQG WZRORZHVWH[FLWHGVWDWHVZHUHDOVRREWDLQHG  7KHVWDWHDYHUDJH&$66&)FDOFXODWLRQVDQG
JHRPHWU\RSWLPL]DWLRQVZHUHGRQHE\0ROFDV  $SUHOLPLQDU\YHUVLRQRI'DOWRQZDVHPSOR\HGIRUVWDWHVSHFLILF&$66&)DQGQXFOHDUVKLHOGLQJFDOFXODWLRQV 
7KHDWRPLFQDWXUDORUELWDO $12 W\SHEDVLVVHWKDVEHHQXVHGIRUDOODWRPV










>@'5RFD6DQMXiQ*2ODVR*RQ]iOH],*RQ]iOH]5DPtUH]/6HUUDQR$QGUpVDQG
00HUFKiQ-$P&KHP6RF  


288

3PP-40

Zero-field splitting tensors of nitroxide-based biradicals:
A theoretical study
Kenji Sugisaki,1 Kazuo Toyota,1 Kazunobu Sato,1 Daisuke Shiomi,1 Shuichi Suzuki,1Keiji Okada,1 Masahiro Kitagawa,2 Takeji Takui1
1
Department of Chemistry, Graduate School of Science, Osaka City University, Japan2
Department of System Innovation, Graduate School of Engineering Science, Osaka
University, Japan
Nitroxide radicals have been widely investigated both experimentally andtheoretically owing to their rich variety of applications in chemistry, biochemistry, andmaterials science. In nitroxide radicals the unpaired electron is almost localized on theoxygen and nitrogen atoms, giving rise to strong spin–orbit couplings. Theoreticalinvestigations of the zero-field splitting (ZFS) tensors (D tensors) of nitroxide-based
biradicals are important because the spin–orbit coupling appears as the second-ordercontribution to the D tensor in perturbation theory starting from non-relativistic
Schrödinger equation. In this work, the spin–orbit and spin–spin terms of the D tensors(DSO and DSS tensors, respectively) of nitroxide-based biradicals 1–3 (Figure 1) areinvestigated by the state-of-the-art quantum chemical calculations.
The Molecular geometries havebeen optimized at the UBP86/6-31G*
level for the lowest triplet state, andthe DSO tensors calculated by a hybrid
Figure 1. Target molecules
CASSCF/MRMP2 approach [1–3],
which has recently proposed by us. The DSS tensors have been computed by using
McWeeny–Mizuno’s equation with the ROBP86/cc-pVDZ spin density [2–3].
The experimental and theoretical ZFS parameters D (D = DZZ – (DXX + DYY)/2) aresummarized in Table 1. For 1 and 2, our calculation can reproduce the experimental D
value within 10% of error. For 3, the calculations significantly overestimate the absolutevalue of D. Since the spin–orbit contribution to D in 3 is ca. 14%, most of errors in thecalculations are possibly Table 1. Theoretical and experimental D values.
from the DSS term. The Molecule DSS/cm–1 DSO/cm–1 DSS+SO/cm–1 |D(Exptl.)|/cm–1
dependence pf the dihedral
1–0.0337+0.0063–0.0376
0.0394angle on the D tensors will2
–0.0590+0.0151–0.0668
0.0639also be discussed.
3–0.0342–0.0035+0.0353
0.0250[1] Sugisaki, K. et al. Chem. Phys. Lett. 2009, 477, 369–373.
[2] Sugisaki, K. et al. ChemPhysChem 2010, 11, 3146–3151.
[3] Sugisaki, K. et al. Phys. Chem. Chem. Phys. 2011, 13, 6970–6980.

289

3PP-41

Density functional theory calculations of iodine cluster anions:structures, chemical bonding nature, and vibrational spectra
Miho Otsuka1, Hirotoshi Mori2, Hitomi Kikuchi1, Keiko Takano1
1
Graduate School of Humanities and Sciences, Ochanomizu University, Japan
2
Division of Advanced Sciences, Ocha-dai Academic Production,
Ochanomizu University, Japan
Ϩ. Introduction
The tendency of iodines to form stable polyiodide anions is well known. A
scientifically interesting feature is their bond property. The idea of a three-center
four-electron (3c-4e) bond to explain the linear electron-rich three-center bond featurein I3- was confirmed with density functional theory (DFT) calculations [1, 2]. The objectof the present study is to elucidate the chemical properties of larger iodine clusters, In(n = 3, 5, 7), in detail.
ϩ. Method
All available equilibrium structures were surveyed using the global reaction route
mapping (GRRM) technique [3] with UB3LYP/LANL2DZ level of theory. Then, thesurveyed structures were refined using MCPtzp+ basis, a larger basis set with a model
core potential [4], to obtain enough accuracy for discussion on chemical bonding nature.
Natural bond orbital (NBO) analysis was applied to analyze the chemical bonds [5] andRaman spectra were also predicted for comparison with experiments.
D∞hϪ. Results and discussion [6]
It was found that all the stable minima of In have asingle or a branched chain structure (Figure 1). There
were no energy minima for cyclic structures. NBO
analysis suggested that In consist of I2 and linear I3
units containing 3c-4e bonds. DFT calculations showedthat In (n = 5, 7) have two types of Raman scattering,in regions 140-190 cm-1 and 110-120 cm-1, which areassigned to the vibrations of I2 and I3 units,
respectively. A comparison of theoretically predicted
Raman spectra with experimental results [7] revealed
the existence of In (n = 5, 7) isomers with 3c-4e bonds.
[1] G. A. Landrum et al. J. Chem. Soc., Dalton Trans.,
1997, 3605. [2] M. L. Munzarova et al. J. Am. Chem.
Soc., Sect. A 1972, A28, 574. [3] S. Maeda et al. Chem.
Phys. Lett. 2003, 381, 177. [4] E. Miyoshi et al. J.
Chem. Phys., 2005, 122, 074104. [5] A. E. Reed et al.
Chem. Rev. 1988, 88, 899. [6] M. Otsuka et al.
Comput. Theor. Chem., submitted. [7] P. H. Svensson Figure 1 Structure of stable
et al. Eur. J. Inorg. Chem., 2000, 1275.
isomers of In- (n = 3, 5, 7)

290

3PP-42

A computational method for infrared reﬂection absorption spectroscopy
Takeshi Iwasa,1,2 Kazuki Horiuchi,2 Masaya Shikishima,2 Yuji Noguchi,2 Shuhei
Nagaoka,2 and Atsushi Nakajima1,2
1
JST, ERATO, Nakajima Designer Nanocluster Assembly Project, 3-2-1 Sakado,
Takatsu-ku, Kawasaki, 213-0012, Japan2
Department of Chemistry, Faculty of Science and Technology, Keio University,
3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan
Infrared reﬂection absorption spectroscopy (IRAS) has been widely used to investigate geometric structures and orientations of molecules at a surface, where theselection rule is diﬀerent from that in gas phase. The electric ﬁeld at a surface mainly
lies along the surface normal due to the interference between the induced and reﬂected light, and thus IRAS peak intensities depend on the molecular orientation.
We present a computational method for IRAS spectrum and a numerical demonstration using Ti(aniline) deposited onto an alkanethiol self-assembled monolayer(CH-SAM) surface.
Geometric structures of Ti(aniline)-C3 H8 from singlet to quintet states are optimized at the B3LYP/def2-TZVP level of theory. The molecular orientation isdetermined by ﬁtting C3 H8 to CH-SAM whose orientation is taken to be 15◦ fromthe surface normal. k-th IRAS peak for these conﬁgurations is computed using thenext formula.

2
 3N
2


 ∂

 

μ
∂μ




· n = 
ck,i
· n
(1)
Ik ∼ 
 ∂Qk



∂bi
i=1
where μ is the dipole moment, Qk is the k-th normal coordinate, n is the unit
vector of the surface normal, ck,i is the transformation matrix from the atomic
displacements bi to Qk . The numerical derivatives ∂μ/∂bi and vibrational frequencies
are obtained using a locally modiﬁed version of SNF 4.01 . We adopt |bi | = 0.01 a.u.
and the scaling factor of 0.977.
As an example, we show (a)IR and (b)IRAS spectra
for the triplet state in Fig. 1. The peak intensity at 1500
and 1405 cm−1 , for instance, decreases and increases, re- (a)spectively, as a result of the orientation. The projectionof ∂μ/∂Qk to the surface normal enables us to directlycompare the IRAS spectrum with experimental results. (b)We will present the IR and IRAS spectra for the otherspin states and comparisons with the experiment to determine the geometric and electronic structures of the1650 1550 1450 1350
Wavenumber (cm-1)
Ti(aniline) deposited onto the CH-SAM.
[1] J. Neugebauer, M. Reiher, C. Kind, and B. A. Hess, Figure 1: IR and IRAS
J. Comput. Chem. 23, 895 (2002).
spectra for the triplet
state.

291

3PP-43

Photoinduced charge-transfer and normal-cleavage reaction of
Mg+-Benzene complex
Kota Daigoku1
1
Division of Chemistry, Center for Natural Sciences, College of Liberal Arts andSciences, Kitasato University, JapanThe magnesium-benzene complex in gas phase provides simple model systems forthe cation-π interaction. For the Mg+-benzene complex, the experimental result of thephotoinduced dissociation reaction shows that the dominant product is not
charge-transfer products, Mg0 and benzene+, but normal-cleavage reaction products,
Mg+ and benzene1. However this selective reaction mechanism is not well understood.
We investigated the potential energy curves of Mg+-benzene complex in the ground andlow-lying excited states at the RASPT2 methods.
The starting points of the dissociation reaction are the 1 2E1(3px,y  3s) and 2
2
A1(3pz  3s) states according to the experiment and theoretical calculations. Theenergy curve of the 1 2E1 state shows the vibrational predissociation and conicalintersection in the Frank-Condon region. The former is correlated to the chargetransfer (3s  π) state and the later is crossing with the 1 2E2 (π*  3s) state. The
transition through the conical intersection will occur prior to the predissociation reaction
because of the ultrafast nonradiative process. As in the case of the 1 2E1 state, thetransition to the 1 2E2 state via the conical intersection will occur prior to the othertransition in the 1 2A1 state. After the nonradiative transition to the 1 2E2 state via
these conical intersections, the curve crossing in the short Mg-benzene distance region
will make the ground-state channel open.
A1, A2 states

B1, B2 states

77

3px,y←π

Potential energy ( eV )

6

5

π*←π
π*←π(T)5

3pz←3s

4

3

6

π*←3s

3px,y←π

4

5

1 A1

2

3

π*←3s

2

1 A2

2

2 2A 1
3 2A 1

1

2.0

2.5

3.0 3.5 4.0
R Mg−Benzene ( Å )3pz←ππ*←π(T)
3px,y←3s

4π*←π(T)32

3px,y←π

π*←π

6

0

E1, E2 states

7

4.5

5.0

1 2B1

2

2

2 B2
3 2B2

1
0

1 2B2

2.0

2.5

2

2 B1

3.0 3.5 4.0
R Mg−Benzene ( Å )

1

4.5

5.0

0

3s←π

1 2E1

1 2E2

2

2 2E2

2 E1
3 2E1
4 2E1
2.0

2.5

3.0 3.5 4.0
R Mg−Benzene ( Å )

4.5

5.0

Figure 1. Potential energy curves of Mg+-benzene complex along the Mg-benzene
distance calculated at RASPT2 level.
[1] X. Yang, K. Gao, H. Liu, S. Yang, J. Chem. Phys. 112, 10236 (2000).

292

3PP-44

Theoretical study on the molecular structures of X-, Į- and ȕ-types oflithium phthalocyanine dimer
Michinori Sumimoto,1 Yukio Kawashima,2 Daisuke Yokogawa,3 Kenji Hori,1 Hitoshi
Fujimoto4
1
Graduate School of Science and Engineering, Yamaguchi University, Japan2
Department of Research Superstar Program, Organization for the Promotion ofAdvanced Research, Kyushu University, Japan
3
Institute for Protein Research, Osaka University, Japan
4
Department of Chemistry, Faculty of Science, Kumamoto University, Japan
It is very important to select a suitable functional for the calculation target using thedensity functional theory (DFT) method. In particular, special care should be taken forweakly bound systems with non-covalent interactions, which require an accurate
assessment of the long-range interaction. Marom and co-workers [1] recently suggested
an approach to treat the long-range interaction in DFT calculations for weakly boundsystems, and applied it to weakly-bound metal phthalocyanine (MPc) dimers with theclosed-shell electron system.
We reported the results of theoretical calculations on the potential energy curves(PECs), geometry optimizations, and electronic structures for three dimers of LiPc and
MgPc using three types of functional systems, PBE1PBE, B3LYP, and M06 [2]. We
discussed how the dispersive interaction affects the geometric and electronic structures of
the LiPc and MgPc dimers. The calculated results provide a clear understanding of thecomputational method for both open- and closed-shell MPc dimers: the PBE1PBE andB3LYP functional systems cannot evaluate a weak dispersion interaction appropriately.
In contrast, the M06 functional can estimate a weak dispersion interaction well in both the
open- and closed-shell MPc dimers. However,
the results should be examined with caution
against overestimation of the relative stabilities.
Basis set superposition error (BSSE) corrections
play an important role for the quantitative
analysis, but the calculation results without
BSSE corrections may be enough for thequalitative discussion of the relative stability.
[1] N. Marom, A. Tkatchenko, M. Scheffler, L.
Kronik, J. Chem. Theory Comput. 2010, 6, 81.
[2] M. Sumimoto, Y. Kawashima, D. Figure 1. PECs for the Į-, ȕ-, and X-type LiPc
dimers, which were obtained by single point
Yokogawa, K. Hori, H. Fujimoto, J. Comput. calculations with the PBE1PBE, B3LYP, and M06
functional systems while varying the Li-Li distance.
Chem. 2011, in press.

The red and black colors show the PECs with andwithout BSSE corrections, respectively.

293

3PP-45$ELQLWLR6WXGLHVRI$URPDWLF([FLPHUV8VLQJ0XOWLFRQILJXUDWLRQ
4XDVL'HJHQHUDWH3HUWXUEDWLRQ7KHRU\

U 55 


6RLFKL6KLUDL6XHKLUR,ZDWD7DNDR7DQL6KLQML,QDJDNL
7R\RWD&HQWUDO5 '/DERUDWRULHV,QF1DJDNXWH$LFKL-DSDQ-67&5(67.DZDJXFKL6DLWDPD-DSDQ
7R\RWD3K\VLFDODQG&KHPLFDO5HVHDUFK,QVWLWXWH1DJDNXWH$LFKL-DSDQ,,QWURGXFWLRQ$URPDWLFH[FLPHUVKDYHEHHQERWKH[SHULPHQWDOO\DQGWKHRUHWLFDOO\LQYHVWLJDWHGLQ
WKH ILHOG RI SKRWRSK\VLFV DQG SKRWRFKHPLVWU\ EHFDXVH RI WKHLU XQLTXH SURSHUWLHV+RZHYHU WKHUH KDYH EHHQ OLPLWHG DE LQLWLR VWXGLHV HYHQ WRGD\ ,Q WKLV VWXG\ ZH
WKHRUHWLFDOO\ LQYHVWLJDWH WKH HOHFWURQLF VWDWHV RI H[FLPHUV RI EHQ]HQH QDSKWKDOHQH
DQWKUDFHQH S\UHQH DQG SHU\OHQH )LJXUH   XVLQJ WKH PXOWLFRQILJXUDWLRQTXDVLGHJHQHUDWHSHUWXUEDWLRQWKHRU\ 0&4'37 IRUV\VWHPDWLFDOXQGHUVWDQGLQJV>@,,&RPSXWDWLRQDO'HWDLOV
7KH UHIHUHQFH FRQILJXUDWLRQ VSDFH IRU 0&4'37 ZDV FDUHIXOO\ GHVLJQHG IRU DQ
DSSURSULDWHGHVFULSWLRQRIWKHWDUJHWHOHFWURQLFVWDWHVZLWKDWUDFWDEOHFRPSXWDWLRQDOFRVW$VVXPLQJ HFOLSVHG SDUDOOHO DUUDQJHPHQWV RI WKH DURPDWLF GLPHUV WKH SRWHQWLDO HQHUJ\FXUYHV IRU WKH JURXQG DQG H[FLPHU VWDWHV WKH ORZHVW /DGHULYHG H[FLWHG VWDWHV  ZHUHFRPSXWHGDVDIXQFWLRQRIWKHLQWHUPROHFXODUGLVWDQFHU 55 IURPWRc,,,5HVXOWVDQG'LVFXVVLRQ
7KHFDOFXODWHGPRQRPHUDEVRUSWLRQHQHUJLHVDQGH[FLPHUIOXRUHVFHQFHHQHUJLHVDUH
LQJRRGDJUHHPHQWZLWKWKHH[SHULPHQWDOYDOXHV 7DEOH 'HWDLOHGDQDO\VLVRIWKHZDYHIXQFWLRQ FRQILUPV WKH PL[LQJ RI WKH H[FLWRQ UHVRQDQFH (5  DQGWKH FKDUJH UHVRQDQFH
&5  VWDWHV ZKLFK DUH UHVSRQVLEOH IRU WKH DWWUDFWLYH QDWXUH RI WZR PRQRPHUV LQ WKH
H[FLWHGVWDWH,QWKHH[FLPHUV(5DQG&5VWDWHVDUHIRXQGWRFRQWULEXWHDOPRVWHTXDOO\WRWKHZDYHIXQFWLRQ7KHUHIRUHWKHRUGHURIELQGLQJHQHUJ\'HLVFRQVLVWHQWZLWKWKH
RUGHUV RI PRQRPHU WUDQVLWLRQ GLSROH PRPHQW DQG ³,RQL]DWLRQ 3RWHQWLDO ± (OHFWURQ$IILQLW\´7KHVHUHVXOWVVXJJHVWWKDWWKHHOHFWURQLFVWDWHVRIWKHVHDURPDWLFH[FLPHUVDUH
DSSURSULDWHO\GHVFULEHGDQGV\VWHPDWLFDOO\XQGHUVWRRGE\XVLQJ0&4'37

7DEOH&DOFXODWHGDQGH[SHULPHQWDOYDOXHV VHHUHI>@
DQG UHIHUHQFHV WKHUHLQ  IRU WKH VHOHFWHG VSHFWURVFRSLF

SDUDPHWHUVIRUWKHORZHVW/DGHULYHGH[FLWHGVWDWHUH'H)OX H9$EV H9
'LPHU

c
H9
&DOF ([SWO&DOF ([SWO %HQ]HQH 







 1DSKWKDOHQH  


 



)LJXUH  $URPDWLF H[FLPHUV  $QWKUDFHQH     WUHDWHGLQWKLVVWXG\ 3\UHQH  





 3HU\OHQH  





>@6KLUDL6,ZDWD67DQL7,QDJDNL6-3K\V&KHP$LQSUHVV'2,MSN 

294

3PP-46

Applying residual minimization method to GIAO-CPHF equation
convergence for calculation of nuclear magnetic shielding tensors
Toshihiko Abe,1 Toshiyuki Hirano,1 Hirotaka Tanimura,1 Fumitoshi Sato1
1
Institute of Industrial Science, The University of Tokyo, Japan
I. Introduction
A new method to robustly solve the coupled perturbed Hartree-Fock (CPHF)
equation for calculation of nuclear magnetic shielding tensors is proposed. The DIIS
method is widely adopted, where it solves the equation projected onto the iterative
subspace[1]. On the other hand, the proposed method seeks the solution in theiterative subspace by the residual minimization method[2] to minimize the residual
deﬁned in the whole orbital space. Compared to general residual minimization
methods (ex.[3]), the proposed one showed the good convergence.
II. Method
The GIAO-based CPHF equation is represented by projection onto the occupied
and the vacant orbitals as follows[4].
occ vac  c+ (F(1,0) − K S(1,0) )cL
1+K
P(1,0) = − P(0) S(1,0) P(0) + 2
× (cK c+L − cL cK ),2
K − L
K(1)

L

where cK and P(0) are the LCAO coeﬃcients and the density matrix that satisfy the
HF equation, respectively. P(1,0) and F(1,0) are the the ﬁrst order perturbed density
and Fock matrix with respect to the external magnetic ﬁeld, respectively. The P(1,0)
is given by solving the CPHF equation. Since F(1,0) depends on P(1,0) , by expanding
all the coeﬃcients the CPHF appears as Hu = b , where u is the vector representationof P(1,0) . H is a supermatrix and usually solved by iterative calculation.
The proposed
method uses the linear combination of vectors in the iterativeLsubspaceu = l kl ul and minimizes the 2-norm of the residual R2 = b − Hu2 =LL2
l,m=1 kl km (Hul ) · (Hum ) − 2
l=1 kl (Hul ) · b + b ; that is,
L


∂R2
=
2kl (Hum ) · (Hul ) − 2(Hum ) · b = 0.
(2)
∂km
l=1

Therefore we solve Ll=1 kl (Hum ) · (Hul ) = (Hum ) · b , which is an Lth-order linear

equation.
III. Results
In the ﬁgure, the computational results of a nitrogen molecule were shown as thenorm of the diﬀerence of P(1,0) to the number of iterations. The simple damping
and method 3 showed good convergence. In principle, the residual is not increasedby the method 3, so that the method 3 might prevent divergence when the simple
damping cannot provide a stable derivative density matrix.
-2• Simple damping

Simple damping
Method 1
Method 2
Method 3-4• Simple residual minimization (Method 1)• Residual minimization with adjusting the damping factor(Method 2)

Log10 |Δ P

(1,0)

|

-6
-8

• Method 2 + normalization (Method 3)

-10
-12
-14
-16
-18

0

10

20

30

40

50
60
Iteration

70

80

90

100

[1] P. Pulay, Adv. Chem. Phys., 69, 241, 1987.
[2] A. Tamura, K. Kikuchi and T. Takahashi, J. Comp. Phys., 137,
247, 1997.
[3] Y. Saad and M.H. Schultz, SIAM J. Sci. Stat. Comput., 7, 856,
1986.
[4] M. A. Freitag, and B. Hillman and A. Agrawal, J. Chem. Phys.,
120, 1197, 2004.

295

3PP-47

A theoretical study on the photodissociation of HNO3 involving S2, S1and S0 states
Hongyan Xiao,1 Satoshi Maeda,1,2 Keiji Morokuma1,3
1
Fukui Institute for Fundamental Chemistry, Kyoto University, Japan
2
The Hakubi Center, Kyoto University, Japan
3
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry,
Emory University, United States
Nitric acid (HNO3) molecule plays an important role in atmospheric chemistry.
Depending on the irradiation wavelength, the photodissociation of nitric acid has richphotochemical decay channels. The common conclusion in experiments (J. Phys. Chem.
1993, 97, 9924; J. Chem. Phys. 1994, 100, 8040; Chin. J. Chem. Phys. 2009, 22, 191) isthat at or near 248 nm the dissociation OH(X 2Ȇ) + NO2(Ã 2B2) on 21A" state (thesecond excited state, S2) is dominant, while at larger wavelength the dissociation OH(X~2Ȇ) + NO2( X 2A1) on 11A" state (the first excited state, S1) is the primary pathway. Withan increase in photon energy, the minor O(1D) product was observed at 222 nm (J.
Chem. Phys. 1992, 96, 5887). In this work, we investigated the photodissociation
mechanism of HNO3 based on CASPT2 calculations using a systemic reaction pathsearch method. Our results indicated that upon photoexcitation with energy higher than
248 nm, elimination OH(X 2Ȇ) + NO2(Ã 2B2) on S2 potential energy surface (PES)~
should be dominant, while at energy below this, fission OH(X 2Ȇ) + NO2( X 2A1) on S1
PES is the primary pathway. In addition, the dissociation pathway to O(1D) on S2 PES
has been found. Our results in general agree with and provide theoretical basis for theexperimental results.
S2-LM1-TS2b
S2-LM1-TS2a
S2-INT
534.6
534.3
532.6
O(1D)+cis-HONO
509.1

S2-GM-TS2b
S2-GM-TS2a S2/S1
533.5
521.2
512.7

S2-TS

S2-LM1-TS1
496.9

501.5
S2-LM1
S2-GM

481.8

O(1D)+
trans-HONO
506.2(490)aS2-GM-TS1
481.5

459.0
S1/S0-1
392.0

S1/S0-2
388.8
S1-GM
OH(X)+NO2(12B2)

S1-TS1
360.2
OH(X)+NO2(12B2)

344.1

328.7
(315)a
OH(X)+NO2(X2A1)

328.7(315)a219.3(200)aS0-GM

a : Exp. dissociation energy

0.0

Figure. Photodissociation HNO3 from S2 ĺ S0 by 3S-CASPT2(12,8)/6-31+G*(kJ/mol)

296

3PP-48
Theoretical Study of Luminescent Vapochromic Complexes Including
AuCu2(NHC)2 Core
Shinya Tsukamoto, Shigeyoshi Sakaki *Fukui Institute for Fundamental Chemistry, Kyoto University, Japan
I. Introduction: Metallophilic interaction by d10-d10 metal contact exhibits interesting
luminescent behavior in many cases. Though a lot of compounds have been synthesized
to date, a complex including AuCu2 core has been limited. Recently, new vapochromic
compounds which contain a AuCu2 core were synthesized. They exhibit different
luminescent color when they are exposed to vapor (Scheme1). In this work, wetheoretically investigated their ground and excited states, coordinations of MeCN and
MeOH, and elucidated the reason why their emission spectra depend on gas molecule.
The bonding nature between Au(I) and Cu(I) will be also discussed.

1; 462nm(blue)

2; 520nm(green)
3; 573nm(yellow)
Scheme 1
II. Method: The geometry optimization was carried out by DFT method with B3PW91
functional. For Au and Cu atoms, triple-zeta basis sets of Stuttgart group with 2f
polarization functions were employed. For other atoms, 6-31G(d) basis sets were used,
where one diffuse function was added to O atom. The emission peak was evaluated as
the S0-T1 energy difference with the T1 geometry.
III. Results and Discussion: The Au-Cu distances of 1 and 2 are 4.742 and 3.174 Å,
respectively, in the S0 ground state, suggesting that gas molecule coordinate with Cu
center influences the Au-Cu contact. Their optimized structures of the T1 state are notsymmetrical; the Au-Cu distances are 4.983, 4.588 Å in 1 and 2.634, 2.609 Å in 2. The
T1 state of 1 was assigned to Cu dÆPy S*. Its calculated emission energy (2.93 eV)agrees with the experimental one (2.68 eV). On the other hand, the T1 state of 2 was
assigned to Au dÆAu-Cu bonding MO (Fig 1), indicating that the Au-Cu bond isformed in the T1 state. This is consistent with the shorter Au-Cu
distance in the T1 state. The calculated
emission energy (2.27 eV) agrees wellwith experimental value (2.47 eV).
Detailed discussion including 3 will bepresented in the poster session.
Fig.1 SOMO of 2 in the T1 state
Reference: [1] Strasser, C. E. et al. J.Am. Chem. Soc 132, 10009, 2010.

297

3PP-49

Intersystem crossing in spin-crossover complexes
Gergely Juhász, Yoshihito Shiota, Kazunari Yoshizawa
Institute for Materials Chemistry and Engineering and International Research Center
for Molecular Systems, Kyushu University, Japan
I. Introduction
Coordination complexes featuring bistability of spin- and electronic states arepotential building blocks for switchable molecular materials. The geometry distortion of
the molecule associated with such spin-transition, however, can be extremely complex
and raise a major challenge for the theoretical description of the switching process. We
demonstrate a new approach, searching the Minimum Energy Crossing Points (MECPs)
on the low-energy energy surfaces in spin-crossover complexes.
II. Method
The calculation of equilibrium geometries, potential energy surfaces (PESs) in thelowest energy spin-states, and the MECPS between them has been performed using
Gaussian 09, Gammes and ORCA programs at B3LYP* / 6-311+G(d,p) level of theory.
III. Results and discussion
For the initial tests, we chose well-characterized spincrossover systems: [Fe(II)(2-pic)3]2+, [Fe(III)(acpa)2]+ , andN[Fe(III)(pap)2]+. Due to the flexibility of the 2-pic ligand, theNH 2
Fe(II) system is close to the ideal octahedral ligand
2-pic
environment, where the low-spin (S=0) to high-spin (S=2)
transition is accompanied with an approximate Δr=0.21 Å bondOFe-N length change. This distortion can be described well alongNN (M)an approximately total-symmetric breathing mode, and the
N (M)
N
O
calculated MECP of the S=0 and 2 states can be wellapproximated along this normal mode. On the other hand, whenpap
acpa
the S=1 intermediates spin state shows a strong Jahn-Teller
effect, therefore axial distortions are also important to describe
the geometry.
The Fe(III) systems with {FeN4O2} chromophores suffer an asymmetric distortion
during the spin transition, as the bond distance change for Fe-N bonds is in order ofΔr=0.18-0.25 Å, while for the Fe-O bonds, it is smaller than Δr=0.4 Å. Careful analysisof the equilibrium and MECP geometries was possible with the new approach, and the
distortions of the coordination environment and the ligands were directly observed.

298

3PP-50

Theoretical study on two-photon absorption properties of
two-dimensionally extended π-conjugated systems
Koji Ohta,1 Satoru Yamada,1 Kenji Kamada,1 Aaron D. Slepkov,2 Frank A. Hegmann,2
Rik R. Tykwinski,3 Laura D. Shirtcliff,4 Michael M. Haley,4 Pawel Sałek,5
Faris Gel’mukhanov,5 Hans Ågren5
1
Research Institute for Ubiquitous Energy Devices, National Institute of Advanced
Industrial Science and Technology (AIST), Japan2
Department of Physics, University of Alberta, Canada
3
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg,
Germany
4
Department of Chemistry and Materials Science Institute, University of Oregon, USA
5
Department of Theoretical Chemistry, School of Biotechnology, Royal Institute ofTechnology, Sweden
R1

R2

Previously, we have measured two-photon
absorption (TPA) spectra of a pair of
two-dimensionallyconjugatedquadrupolar
donor/acceptor (D/A) chromophores, TPEB
[tetrakis(phenylethynyl)benzene] (R1, R2, R3,
R3
R4
R4=Donor(D) or Acceptor(A) in Figure 1) by the
femtosecond Z-scan method [1] and found that these Figure 1. Molecularcompounds display large TPA cross sections. In this structure of TPEBs.
study, to clarify the mechanisms of the TPA process, the TPA properties have beentheoretically investigated by the TDDFT methods [2]. All the excited state properties
were calculated by the TDDFT/B3LYP method using the DALTON 2.0 program. The
one-photon absorption (OPA) and TPA spectra were simulated by the methods reported
previously [3]. In the experimental spectra of the noncentrosymmetric TPEBs(R1=R3≠R2=R4 and R1=R2≠R3=R4), the shape of the OPA and TPA spectra differs
considerably from each other, even though the TPA transitions should occur to the same
excited states where the OPA transitions occur because of the noncentrosymmetry ofthese molecules. For example, the largest OPA band appears around 3.8-3.9 eV, but thecorresponding TPA bands do not appear in the spectra. Calculations for the TPEBs
reveal that this discrepancy results from the destructive interference between the
different transition paths in TPA.
[1] A. D. Slepkov, F. A. Hegmann, R. R. Tykwinski, K. Kamada, K. Ohta, J. A.
Marsden, E. L. Spitler, J. J. Miller, and M. M. Haley, Opt. Lett. 31, 3315 (2006).
[2] K. Ohta, S. Yamada, K. Kamada, A. D. Slepkov, F. A. Hegmann, R. R. Tykwinski,
L. D. Shirtcliff, M. M. Haley, P. Sałek, F. Gel’mukhanov, and H. Ågren, J. Phys. Chem.
A. 115, 105 (2011).
[3] K. Ohta and K. Kamada, J. Chem. Phys. 124, 124303 (2006); K. Ohta, L. Antonov,
S. Yamada, and K. Kamada, J. Chem. Phys. 126, 084504 (2007).

299

3PP-51

Structures and Binding Properties of Noble Gas Compounds:
NgBeO and NgBeOBH3 (Ng = He, Ne, Ar)

Hitomi Suto,1 Hirotoshi Mori, 2 Keiko Takano1
1
Graduate School of Humanities and Sciences, Ochanomizu University, Japan
2
Division of Advanced Sciences, Ochanomizu University, Japan
I. Introduction
After the first experimental observation of a novel neutral xenon compound, XePtF6[1], noble gas containing molecules had kept considerable chemical interests and had
been extensively studied from both experimental and theoretical point of views. Amongthe studies, the existence of neutral He containing systems is still in question, since nosuch a system has been observed experimentally. Frenking et al. and Takayanagi et al.
predicted the presence of the neutral light noble gas compounds, NgBeO (Ng = He, Ne,Ar), using the MP4 and CASPT2 levels of ab initio electronic structure calculations,
respectively [2,3]. In this study, we tried to have a further chemical insight to predict theexistence of the neutral noble gas containing compounds.
II. Computational details
The electronic structures of BeO, NgBeO and NgBeO-BH3 (Ng = He, Ne, Ar) werestudied by CCSD(T), CASPT2, CASPT3 and MRSDCI levels of theory, which are
implemented in the MOLPRO program package. In the multi-reference calculations, 6
electrons were distributed in 7 active orbitals. Two types of basis sets, aug-cc-pVQZ and
aug-cc-pCVQZ, were used. All core electrons were frozen for the aug-cc-pVQZ basis,
meanwhile, Be(1s) core electrons were frozen and correlated with valence electrons forthe aug-cc-pCVQZ basis.
III. Results and Discussion
Table 1 Be-O bond length with the CASPT3 level of theory [ഺ]Table 1 lists theaug-cc-pVQZ a) aug-cc-pCVQZa) aug-cc-pCVQZb)
exp.
㩷㩷
Be-O bond lengths
BeO
1.3356
1.33531.33061.3308
obtained by CASPT3
1.33021.33001.3256levelsoftheory. He-BeO
1.33151.3312
1.3268㩷Compared with the Ne-BeO
experimental results, Ar-BeO
1.33351.3332
1.3289㩷the calculation takinga) with frozen core b) without frozen core
into account the core-valence correlation effect from Be(1s) showed extremely highaccuracy for BeO. This result indicates that not only Be(2s) but also Be(1s) plays animportant role for the BeO bonding, presumably due to the bond polarity ascribed toelectronegativity of O. As for the NgBeO (Ng = He, Ne, Ar), the role of Be(1s) would
be more important because noble gases may affect the Be(1s) as well as the Be(2s).
Essential factors for the stabilization by binding of noble gases will be discussed indetails with the results of NgBeOBH3.
[1] Bartlett, N. Proc. Chem. Soc., 218(1962)[2] Frenking, G.; Koch, W.; Jurgen, G.; Cremer, D. J. Am. Chem. Soc. 110, 8007(1988)[3] Takayanagi, T.;Motegi, H.; Taketsugu, Y.; Taketsugu, T. Chem. Phys. Lett. 454, 1(2008)300

3PP-52

Theoretical Study of Inverted Sandwich Type Dinuclear
Complexes of ethylene and dinitrogen molecules
Masayuki Nakagaki,¶ Yusaku I. Kurokawa,§ and Shigeyoshi Sakaki¶
Fukui Institute for Fundamental Chemistry, Kyoto University, Japan§
Quantum Chemistry Research Institute, Japan¶

I. Introduction
Inverted sandwich type complexes (ISTCs) of dinuclear three-coordinate chromium(I)with DDP ligand, (DDPH = 2-{(2,6-diisopropylphenyl)amino}pent-2-ene), weresynthesized by Tsai et al. 1 and Monillas et al.2 Interestingly, the effective magnetic
moment significantly depends on the metal and sandwiched organic molecule. In thisstudy, we investigated the electronic structure of the ISTCs of ethylene and dinitrogenmolecules.
II. Computational Details
We replaced the DDP ligands with AIP (AIPH = 1-amino-3-imino- prop-1-ene;
SCHEME 1) for brevity. Geometry optimization was carried out for each spin states by
the DFT method with B3LYP functional. The total energies were evaluated by the DFT,CASSCF, and MRMP2 methods. The active space consists of the d-orbitals of two
metals and π* orbital(s) of ethylene and dinitrogen molecules.
III. Results and Discussion
The geometrical parameters optimized by the B3LYP method agree with experimental
value. Table 1 shows the relative energies of various spin states of (P-C2H4) [M(AIP)]2.
Though the high spin state is stable in the B3LYP computational results, the singlet or
triplet states are stable in the MRMP2. The effective magnetic moment (μeff) of(P-C2H4) [Cr(AIP)]2 estimated by MRMP2 is 1.8 μB. This value is smaller than theexperimental value (4.2 μB), indicating that the MR-MP2-calculated stability of thequintet state is underestimated. On the other hand, the μeff (2.6 μB) of (P-N2)[Cr(AIP)]2
is close to the experimental value (3.9 μB). We will present discussion about therelation between spin multiplicity and bonding nature.
TABLE 1. Relative energies of spin states of (μ2-η2:η2-C2H4)[M(AIP)]2 (M=Sc-Cr) calculated by MRMP2 and B3LYP (inparentheses) method (in kcal/mol)

SCHME1:(μ2-η2:η2-C2H4)[M(AIP)]2

11tet
9tet
7tet
5tet
3let
1let

Sc

Ti

V

74.4 (34.3)
2.1 (0.0)
0.0 (18.3)

27.8 (44.7)
2.4 (0.0)
0.0 (35.2)
2.3 (27.0)

63.3 (27.0)
5.2 (0.0)
2.4(46.1)
1.9(25.3)
0.0(64.7)[1] Y.-C. Tsai et al., J. Am. Chem. Soc. 2007, 129, 8066.
[2] W. H. Monillas et al., J. Am. Chem. Soc. 2007, 129, 8090.

301

Cr
14.2 (30.9)
8.7 (0.0)
3.7 (66.6)
2.8 (51.2)
0.0 (117.1)
0.1 (100.4)

3PP-53

Theoretical Study of the Mechanism of Valence Tautomerism in
Cobalt Complexes
Yoshihito Shiota,1 Daisuke Sato,1 Gergely Juhász,1,2 Kazunari Yoshizawa1,21Institute for Materials Chemistry and Engineering, Kyushu University, Japan
2
International Research Center for Molecular Systems, Kyushu University, Japan
I. Introduction
Valence tautomeric (VT) complexes have attracted much attention recently becauseof their possible application as new molecular devices like memory or display devices.
VT complexes show a ligand-metal electron transfer coupled with a spin change on thecentral metal ion, which can be switched by external stimuli like light, heat, or pressure.
We use a model for the cobalt bis(quinone) complex [CoIII(3,5-dbcat)(3,5-dbsq)(bpy)](cat: catecholate, sq: semiquinon, and bpy: 2,2’-bipyridine), which was first reported by
Buchanan and Pierpont in 1980. The complex is in the CoIII-LS form (LS: low-spindoublet state) below 273 K, and the population of the CoII-HS form (HS: high-spin sextet
state) starts with increasing temperature.
II. Method of calculation
Energy calculations for the [CoII-HS(sq)2(bpy)] and [CoIII-LS(sq)(cat)(bpy)]
complexes in the doublet, quartet, and sextet spin states were carried out by using theB3LYP* functional (with 15% Hartree–Fock exchange) implemented in the program
packages Gaussian 03 and GAMESS. For the Co atom, the (14s9p5d)/[9s5p3d]
primitive set of Wachters-Hay with one polarization f-function ( = 1.117) and for the
H, C, N, and O, the 6-311G** basis set were used.
III. Results and discussions
Valence tautomerism is studied in [CoII-HS(sq)2(bpy)]/[CoIII-LS(sq)(cat)(bpy)]
mononuclear cobalt complex by using DFT methods. Calculations at the B3LYP* levelof theory reproduce well the energy gap between the CoII-HS and CoIII-LS forms, giving
an energy gap of 4.4 kcal/mol, which is comparable to an experimental value of 8.9
kcal/mol. Potential energy surfaces and crossing seams of the electronic states of the
doublet, quartet, and sextet spin states are calculated along minimum energy paths
connecting the energy minima corresponding to the different spin states. Calculated
minimum energy crossing points (MECPs) are located 8.8 kcal/mol in the doublet/sextet
surface, 10.2 kcal/mol in the doublet/quartet surface, and 8.4 kcal/mol in thequartet/sextet surface relative to the doublet ground state. Considering the energy of thethree spin states and the crossing points, the one-step relaxation between the CoII-HS and
CoIII-LS forms is the most probable. This research shows that mapping MECPs can be auseful strategy to analyze the potential energy surfaces of systems with complex
deformation modes.
[1] D. Sato, Y. Shiota, G. Juhász, and K. Yoshizawa, J. Phys. Chem. A 2010, 114,
12928-12935.

302

3PP-54

Density functional study of NO binding to Co-center in N2S2
coordination environment
Yuko Wasada-Tsutsui,1 Zhang Zizheng,1 Hiroaki Wasada,2 Tomohiro Hashimoto,2 Takuma
Yano,1 Tomohiko Inomata,1 Yasuhiro Funahashi,1 Tomohiro Ozawa,1Hideki Masuda1
1
Nagoya Institute of Technology, Gokiso-cho Showa-ku, Nagoya 466-8555, Japan
2
Faculty of Regional Studies, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan
Diatomic molecules with 14, 15, and 16 valence electrons, such as CO, NO, and O2
molecules and ions, binding to metals at active sites of enzymes, play an important role inbiological processes. There are many calculations for binding energies of these molecules
to Fe-center of heme to investigate their different affinities. A NO molecule, known as anoninnocent ligand, behaves as NO+, NO, or NO– in coordination compounds and has highNO affinity to later member of the transition metals.
Fe and Co cations centered at the active site of nitrile hydratase (NHase) have a uniquecoordination environment constructed from N and S donor atoms. It is expected that thiscoordination environment should help the metal center in sensitizing NO molecules as wellas in catalyzing a hydration process of nitriles. High sensitivity to NO is expected for Cotype NHase analogue. A binding energy is a convenient probe of affinity to the Co-centerin NHase.
In this work, we studied NO binding mode to Co-centered N2S2 complexes of NHase
analogues using density functional method. We calculated binding energies of the sometypical small molecules of the spectrochemical series to two complexes having different
number of amido-type N atom (Figure 1) in order to elucidate effects of electron donationand charge on the NO selectivity. The calculation shows that the binding energies of a NO
molecule are larger than those of a NH3 molecule, especially those to the coordination
environment having more amido-type N atoms.
We also examine binding energies to [Co(NH2)k(HS)l(NH3)m(H2S)n](3–k–l)+ (k+l+m+n=4)
modeled on NHase analogues to explain NO selectivity based on electronic structure
theory.
O

NH

N

O
N

CoIII

N

O

CoIII
S

S
S

Figure 1.

S

Co-centered N2S2 complexes of NHase analogues

303

3PP-55

DFT study of the properties and formation mechanism of
2-hydroxyterephthalate dianion
Nobuaki Tanaka, Shigeo Itoh, Hiromasa Nishikiori
Department of Environmental Science and Technology, Faculty of Engineering,
Shinshu University, Japan
Blue fluorescence of 2-hydroxyterephthalate dianion (HTP) has been utilized as aprobe of OH radical generation in aqueous solution where the HTP is generated by thereaction of terephthalate dianion with OH radical. This method is widely used in theradiochemical, sonochemical and photocatalytic reaction. In this study we will focus on
the structure and formation mechanism of HTP.
The molecular structure of HTP in water was optimized using density functional
theory, that is, the B3LYP and M06-2X functionals. On the CringCringOH torsion
potential energy curve of HTP two minima were found corresponding to the planar
intramolecular hydrogen bonding and the nonplanar nonhydrogen bonding forms.
Vertical excitations energies were calculated by time-dependent density functional
theory and compared with the experimental data.
The addition reaction of the OH radical to terephthalate dianion is also considered.
All possible reaction sites were included.

304

3PP-56

Theoretical Interpretation of the Photophysical Properties of[n]Cycloparaphenylenes
Cristopher Camacho Yasutomo Segawa Kenichiro Itami Stephan Irle
Department of Chemistry, Nagoya University, Nagoya 464-8601, Japan
The photophysical properties of cycloparaphenylenes are studied and analyzed
by means of time-dependent density functional theory (TD-DFT) as well as molecular dynamic simulations in conjunction with the time-dependent self-consistentcharge density-functional tight binding [1] (TD-SCC-DFTB) and TD-DFT methods. TD-DFT energetics employ the CAM-B3LYP exchange-correlation functional[2] with the def-SV(P) basis set [3]. The features observed in the absorption andemission spectra of [n]CPPs are studied and assigned. A doubly degenerate E stateis responsible for the strong absorption observed in the UV-vis spectra; while its
distorted Jahn-Teller components are responsible for the strong emissions recordedin the ﬂuorescence spectra. It is also found that dynamic eﬀects play an importantrole in the proper description of the features observed in the emission spectra of[n]CPPs.

[1] T. A. Niehaus, S. Suhai, F. Della Sala, P. Lugli, M. Elstner, G. Seifert, and Th.
Frauenheim, Phys. Rev. B, 63, 085108 (2001).
[2] T. Yanai, D. P. Tew, and N. C. Handy, Chem. Phys. Lett., 393, 51 (2004).
[3] A. Schaefer, H. Horn, and R. Ahlrichs, J. Chem. Phys., 97, 2571 (1992).

305

3PP-57

NMR calculations of transition metal complexes
containing MŁP triple bondTerutaka Yoshizawa, Shigeyoshi Sakaki
Fukui Institute for Fundamental Chemistry, Kyoto University, Japan
I. Introduction
Transition-metal complexes containing a multiple bond with non-transition metalelements (e.g. P, Si) have attracted much attention not only due to their exotic naturearising from their unusual bonding characteristics but also due to their interesting
electronic and photophysical properties. To understand well them, their electronic
structure and bonding nature should be investigated well. NMR chemical shifts canprovide important information about the electronic structure and bonding nature. In thepresent study, we theoretically investigated the electronic structures, bonding nature,
and NMR chemical shifts of [(i-PrPhƎN)3MoŁP], [(i-PrPhƎN)3WŁP], and[(R‫މ‬PhƎN)3NbŁP]í (i-Pr = CMe2H, PhƎ = 3,5-Me2C6H3, and R‫( = މ‬CH3)3CCH2)
including the MŁP triple bond, where we employed density functional theory andrelativistic Hamiltonian (second-order Douglas–Kroll–Hess method).
II. Computaional details
We substituted i-Pr, PhƎ, and R‫ މ‬of the real complexes for H in order to reduce the
CPU time. Geometries of the PMo(NH2)3, PW(NH2)3, and PNb(NH2)3í were fully
optimized with the B3LYP functional. LANL2DZ was employed for M and6-31+G(3df,3pd) for the other atoms. The chemical shift į(P) was evaluated with the
B3LYP, where well-tempered basis set and Sapporo-TZP with diffuse functions were
employed for W and the other atoms, respectively.
III. Results
Optimized geometries agree with experimental Table 1. Calculated NMR chemical
ones (Fig. 1). NMR chemical shifts į(P) for three shifts į(P) and experimental values
model complexes and experimental values are shown (ppm) for the model complexes.
Modelį(P)a,b㻌
Exptl.
in Table 1. The calculated į(P) values are not bad,considering that rather small model was employed. It PMo(NH2)3 1503 (1570)㻌 1256
is noted that experimental į(P) values decrease in the PW(NH ) 㻌 1142 (1353)㻌 1021
2 3order Mo > W > Nb, and the decreasing trend is949.2
reproduced well by theí
PNb(NH2)3 1126 (1198)㻌 1019.8
calculations. We will discuss
1110.2
scalarrelativistic
anda
H3PO4 was taken as a standard.
spin-orbit effects for the į(P)b
Scalar relativistic Hamiltonian wasvalues and the relation
used. The values in parentheses are
between the MŁP triple bondestimated with non-relativisticand į(P).
Fig.1 PMo(NH2)3.

306

Hamiltonian.

3PP-58

Calculation of magnetic constants D in Zero-Field Splitting by abinitio methods
Takashi Kawakami, Keiji Kinoshita, Akira Ito, Yasutaka Kitagawa, Shusuke Yamanaka,
Kizashi Yamaguchi, Mitsutaka Okumura
Graduate School of Science, Osaka University, JapanThe magnetic anisotropy is an important property of radicals.
anisotropy Hamiltonian can be expressed as

The magnetic

H = D(Sz2 - S2) / 3 + E(Sx2 - Sy2)
where D and E are axial and transverse zero-field splitting (ZFS) parameters. This
interaction is due to spin-spin coupling (SS) and second-order spin-order coupling(SOC).
For theoretical treatments of ZFS parameters, previously Pederson and co-workers
have developed a method calculating the ZFS parameters with the DFT methods. In
the series of our studies, we developed new ab initio MO program package ("Q" by Ryo
Takeda in our group). The Pederson's treatments are also included in this program.
Thus, several ab initio MO methods can be applied to calculating zero-field splitting
parameters caused by mainly spin-orbit coupling.
We examine the behavior andtendency of the method by applying it to some basic molecules such as small molecules(ex. carbene), pure organic molecular magnets, single-molecular magnets (SMM),
etc.[1-4] It shows the method has good accuracy.
We suggest applicable region of
the method.
In addition, Neese has also developed another calculation scheme withcoupled-perturbed equation.
This method is involved in their program package"ORCA". Thus, we also evaluated ZFS parameters by Neese's methods.

[1] R. Takeda, M. Shoji, S. Yamanaka, K. Yamaguchi, Polyhedron, 24 (2005) 2238.
[2] R. Takeda, K. Koizumi, M. Shoji, S. Yamanaka, M. Okumura, K. Yamaguchi,
Polyhedron, 26 (2007) 2309.
[3] R. Takeda, S. Yamanaka, K. Yamaguchi, Int. J. Quant. Chem., 102 (2005) 80.
[4] R. Takeda, S. Yamanaka, M. Shoji, K. Yamaguchi, Int. J. Quant. Chem., 107 (2007)
1328.

307

3PP-59

Multiple core ionizations and their relaxation process
induced by X-ray free-electron laser irradiation
Yutaka Imamura,1 Takaki Hatsui2
1
School of Advanced Science and Engineering, Waseda University, Japan
2
XFEL Research and Development Division, RIKEN, Japan
Introduction X-ray free-electron laser (XFEL) facilities have enabled to produce laser
pulses strong enough to fully ionize the molecules in short-wavelength regime. Multiple
photoionization of core electrons by XFELs then produces molecules with holes in any
orbitals. XFELs thus provide a new opportunity to investigate the excited states ofmultiply ionized molecules such as ionized states with multiple holes in inner-valenceorbitals. In this paper we have studied theoretically multiply ionized states of aromatic
molecules and subsequent valence excitations.
Result & Discussion Multiply ionized states and their valence excitations of two
aromatic molecules such as aniline and pyridine molecules are investigated. Multiply
ionized states are calculated by the ǻSCF method based on density functional theory(DFT) with the B3LYP exchange-correlation functional. The valence excitations arecalculated by time-dependent density functional theory/Tamm-Dancoff approximation(TDDFT/TDA).
The single and double ionizations of N1s electrons are examined. Let us discuss
effects on orbital energies by the ionizations. For both molecules, the ʌ orbitals around
HOMO are relatively stabilized by the ionizations. The ı* (Rydberg) orbitals around
LUMO are significantly stabilized in comparison with the ʌ and ʌ* orbitals for theionized states of aniline. This is attributed to the fact that the ionizations occur at the N
atom and its stabilization is large for the ı* (Rydberg) orbitals localized around the N
atom. On the other hand, this is not the case of pyridine because the N atom is a part ofthe six-member ring and provides a different picture of the orbitals. Therefore, the
HOMO-LUMO gap for aniline is reduced because of the significant stabilization of theı* LUMO, whereas that for pyridine is not affected significantly.
Next we examine valence excitations for the multiply ionized states. As is predictedfrom the HOMO-LUMO gap for pyridine, the excitation energies do not change
considerably. On the other hand, those for aniline drastically red shift and demonstrate
the possibility that the doubly ionized state of aniline molecule can absorb visible light.
The systematic investigation against other molecules and experiments for visible lightabsorption will be discussed in the poster presentation.

308

3PP-60

Characteristic Fluxional Behavior and Bonding Natureof Hydrogen-bridged Bis(silylene) Complexes
Nozomi Takagi1, Yuto Odagiri2, Hisako Hashimoto2,
Hiromi Tobita2, Shigeyoshi Sakaki1*
1
Fukui Institute for Fundamental Chemistry, Kyoto University, Japan2
Department of Chemistry, Graduate School of Science, Tohoku University, Japan
Hydrogen-bridged bis(silylene)tungsten complexes (1 – 3
in Scheme 1) are of considerable interest, because thesecomplexes are considered as a model of the transition state in
H/D exchange of methane and silane by Cp2MR (M = Ln; R =H, CH3, SiH3) [1]. The variable temperature 1H NMR spectra
show dynamic behavior involving site-exchanges ofsubstituents (R1 to R4). Interestingly, only in 3 two different
types of processes, the cis/trans-exchange (Process I) and thetrans/trans-exchange(ProcessII),
wereobserved
independently and simultaneously depending on thetemperature, though only Process I was observed in 1 and 2.

R1
OC

R2
Si

W

H
Si

OC
R3

R4

1 : R1 = H, R2 = tBu, R3 = R4 = Me
2 : R1 = R3 = R4 = Me, R2 = tBu
3 : R1 = R3 = Me, R2 = R4 = tBu
Scheme 1

Process I
tBua

Mea
OC
W

tBua
OC

Si
H

Meb

OC

Mea

OC

tBub

Si

tBub

Meb

tBua

Meb
OC

Si

Meb
Mea

1,3-Me migration

OC

tBua

Meb

H

OC

Mea

OC

W
Si

OC

tBub

1,3-Me migration

cis-3

H

Si
W

W

Si

OC

tBua

H
Si

Si
W

Si

tBub

H
Si

tBub

Mea

trans-3

Scheme 2

Here, we investigated the mechanism of the dynamic behavior by density
functional theory and post-Hartree-Fock calculations. Our calculations indicate that in
the Process I the 1,3-Me migration occurs easier than the W=silylene rotationsee
Scheme 2 for these steps. In the Process II, the hydrogen-bridged bis(silylene) unit
rotates with the smaller activation barrier than that of Process I (Scheme 3). This result
agrees well the experimental fact that the Process II takes place at lower temperaturethan the Process I. The details of the reaction
Process II
features as well as the characteristic bonding
Me
tBu
Me
tBu
features of the three-center interaction of Si-H-Si,
OC
OC
Si
Si
the W-Si double bonding nature, and the rather
W
H
W
H
Si
Si
short Si-Si distance will be presented.
OC
OC
a

a

b

tBub

Meb

tBua

trans-3trans-3'
Scheme 3bMea[1] (a) L. Perrin, L. Maron, O. Eisenstein, Inorg. Chem., 2002, 41,4355. (b) L. Maron, L. Perrin, O. Eisenstein, Dalton. Trans.,
2003, 4313. (c) L. Perrin, O. Eisenstein, L. Maron, New J. Chem.,
2007, 31, 549.

309

3PP-61

SAC-CI Study on Excitation Spectra of Doublet Molecules
Yasushi Honda, Tadamasa Shida, Hiroshi Nakatsuji
Quantum Chemistry Research Institute (QCRI)
CREST, Japan Science and Technolocy (JST) Agency
Shida, one of the authors, has developed a method for spectroscopy of radical
molecules and succeeded in observations of excitation spectra for a large number oforganic doublet radicals [1]. However, the natures of the spectral bands are still unknown
or uncertain. In this study, we calculated excitation spectra of several organic cation andanion radicals using the Symmetry Adapted Cluster (SAC)/SAC-Configuration
Interaction (SAC-CI) theory to obtain reliable interpretations of their spectral bands.
As the examples, the calculation results of the excitation spectra for cation radicals
of polyenes CH2(CHCH)nCH2 (n = 1-3) and tetracyanoquinodimethane (TCNQ) anion
radical are shown below. The calculated spectra are in good agreement with theexperimental ones. The spectral bands with lower and higher
energies for polyene cation radicals are in+common assigned to S-SSOMO and SSOMO-S*transitions, respectively. Lower-energy shiftof the peaks accompanied by the chain
elongation is due to unstabilization of theoccupied orbitals. For TCNQ, the peak at ca.
40000
30000
20000
10000
23000 cm-1 in the experimental spectrum was
Excitation Energy / cm-1
uncertain. Our calculations reproduced this+peak at ca. 24000 cm-1 and is assigned to the
SSOMO*-S* excitations.
[1] T. Shida, Physical Sciences Data 34 “Electronic
absorption spectra of radical ions”; Elsevier, 1988.
40000

30000
20000
Excitation Energy / cm-1

10000

㩷
+

40000

30000
20000
Excitation Energy / cm-1

10000

40000

30000
20000
10000
Excitation Energy / cm-1

Figure. Excitation spectra of polyene cation (left) and tetracyanoquinodimethan (TCNQ) anion (right) radicals
calculated by SAC-CI together with their experimental ones.

310

3PP-62

7KHLQWHUQDOFRQILJXUDWLRQLQYHUVLRQRI2UWKRSKHQ\OHQHGHULYDWLYH$]XVD0XUDRND +LURVKL8VKL\DPD.RLFKL<DPDVKLWD

6FKRRORI6FLHQFHDQG7HFKQRORJ\0HLML8QLYHUVLW\-DSDQ'HSDUWPHQWRI&KHPLFDOV\VWHPHQJLQHHULQJ7KH8QLYHUVLW\RI7RN\R-DSDQ,,QWURGXFWLRQ
3RO\SKHQ\OHQH QDQRVWUXFWXUHV DUH HVWDEOLVKHG LQ RUJDQLF PDWHULDO FKHPLVWU\ ,Q
VKDUSFRQWUDVWWRH[WHQVLYHO\VWXGLHGSDUDDQGPHWDFRQQHFWHGDQDORJXHVKRZHYHURUWKRSKHQ\OHQH KDYH EHHQ UHFRJQL]HG DV DQ HOXVLYH FODVV RI SVWDFNLQJ FRPSRXQGV 5HFHQW\HDU2KWDHWDOGHPRQVWUDWHGVXFFHVVIXOHODERUDWLRQRIPXOWLSOHRUWKRSKHQ\OHQHV\VWHP> @ :H LQYHVWLJDWH WKH RUWKR SKHQ\OHQH GHULYDWLYH ZKLFK LQFOXGHG HLJKW SKHQ\OHQH
XQLWV DQG QLWUR JURXS DW WKH WHUPLQDO SRVLWLRQV $OWKRXJK WKHVH FRQIRUPDWLRQ KDV WKHFRQQHFWLRQZLWKWLJKWDQJOHGDURPDWLFXQLWVRUWKRSKHQ\OHQHGHULYDWLYHVGLVSOD\HGDYHU\
IDVWKHOLFDOLQYHUVLRQSURILOHLQVROXWLRQ >@$VIRUWKHUHDVRQVIRUUDSLGLQYHUVLRQ ZH
LGHQWLI\ WKH G\QDPLF DVSHFW RI SVWDFNLQJ LQ UHODWLRQ WR D WKHRUHWLFDO QRWLRQ WKDWFRQGHQVHGSFORXGVDUHUHSXOVLYHWRRQHDQRWKHUEHWZHHQQHXWUDODQGFDWLRQLFPROHFXOHV ,,5HVXOWVDQG'LVFXVVLRQV:H UHODWHGFRQIRUPDWLRQDOWUDQVLWLRQRIWKHKHOLFDOJHRPHWU\LQQHXWUDODQGFDWLRQLF
RI RUWKR RFWDSKHQ\OHQH GHULYDWLYH XVLQJ DE LQLWLR 02 FDOFXODWLRQV DW WKH GHQVLW\IXQFWLRQDO WKHRU\ DW %/<3 OHYHO DQG H[DPLQHG LQWHUSODQDU URWDWLRQDO DQJOHV DQGGLVWDQFHVEHWZHHQDGMRLQLQJSKHQ\OHQHXQLWVDQGDFWLYDWLRQHQHUJ\ VKRZQ DV )LJ :H
GLVSOD\HG WKDW WKH RUWKR SKHQ\OHQH GHULYDWLYHV GLVSOD\HG D YHU\ IDVW KHOLFDO LQYHUVLRQSURILOH DQG GHVFULEHG WKDW LW LV DFWLYDWHG LQ RUGHUWR G\QDPLFDOO\ PLQLPL]H D UHSXOVLYH
IRUFH RSHUDWLYH EHWZHHQ WKH FRQGHQVHG SFORXGV ,W LV FRQVLGHUHG WKDW WKH HOHFWURQUHSXOVLRQEHFRPHVZHDNHULQPROHFXOHVOHDGLQJWRUHGXFHGLQWHUSODQDUGLVWDQFHVEHWZHHQ
WKHFRIDFLDOSKHQ\OHQHXQLWV







D 1HXWUDO                          E &DWLRQLF
)LJ*HRPHWU\RIQHXWUDODQGFDWLRQLFRUWKRSKHQ\OHQHGHULYDWLYH>@(2KWD+6DWR6$QGR$.RVDND7)XNXVKLPD'+DVKL]XPH0<DPDVDNL.
+DVHJDZD $ 0XUDRND + 8VKL\DPD . <DPDVKLWD 7 $LGD 1DWXUH &KHP   (<DVKLPD1DWXUH&KHP  >@-+H-/&UDVH6+:DGXPHWKULJH.7KDNXU/'DL6=RX55DWKRUH&6
+DUWOH\ - $P &KHP 6RF     &6+DUWOH\-+H-2UJ&KHP
  

311

3PP-63

Time dependent quantum dynamical simulations of C2
condensation under extreme conditions
Jacek Jakowski∗
National Institute for Computational Sciences,
JICS-ORNL, One Bethel Valley Road,
Bldg 5100 ms 6173, Oak Ridge, TN 37831, USA

Stephan Irle
Institute for Advanced Research and Department of Chemistry,
Nagoya University, Nagoya 464-8602, Japan

Keiji Morokuma
Fukui Institute for Fundamental Chemistry,
Kyoto University, Kyoto 6006-8103, Japan
We report theoretical studies of initial phase of condensation of bulk C2 into carbon nano-structures by means of Born-Oppenheimer and time-dependent quantum
mechanical Liouville-von Neumann molecular dynamics employing density functionaltight binding framework for electrons. We observe that the time-dependent quantum
mechanical approach leads to faster formation of carbon nano-structures than analogous Born-Oppenheimer simulation. Our results suggest that the condensation of
bulk carbon is non-adiabatic in its nature with the critical role of electronic stopping
as in ion-irradiation of materials. Contrary to time-dependent quantum mechanicalsimulations, Born-Oppenheimer dynamics incorrectly predict that the short carbon
chains obtained from initial reactive collisions between C2 quickly evaporate, leading
to much lower probability of secondary collisions and condensation. We also discuss
some deﬁciencies in Born-Oppenheimer dynamics that leads to unphysical chargepolarization and electron transfer.

∗

Electronic address: jjakowsk@utk.edu

312

3PP-64

Theoretical study on angular momentum polarization ofphotofragment of ICl
Takahide Matsuoka1㸪Oonishi Sayo1㸪Satoshi Yabushita1
1School of Fundamental Science and Technology, Keio University, Japan[Introduction] In a photoexcitation process, a linear molecule can be excited simultaneously
to different electronic states after a mixed transition with parallel (//) and perpendicular (ԋ)
components. If these two excited states are led to an identical quantum state of thephotodissociation products, their angular momentum polarization, which is a distribution ofmJ, the fine structure levels, contains the coherent component, i.e. interference between the de
Broglie waves for the different photodissociation processes, which reminisces Young's double
slit model. Thus, the wavelength dependence of the angular momentum polarization contains
the information of transition dipole moment (TDM), potential energy curve (PEC), andnonadiabatic coupling term (NACT). The objective of this study is to investigate thedynamics of photodissociation processes by evaluating angular momentum polarization
parameter in theoretical methods, and comparing the results with experimental data to assess
their accuracy.
[Theory and Method] Spin-orbit configuration interaction (SOCI) calculations were done foreach electronic state with the COLUMBUS program package. For PEC, second-order CI
calculations were performed and Davidson corrections were included. For first-order NACT,
only the CI contribution was considered, and was calculated with the numericaldifferentiations (ΔR=0.005 bohr) of CI coefficients. First-order CI wavefunctions were
employed for TDM. The dynamics calculations were done by the wavepacket method
employing the Chebychev expansion method.
[Results and Conclusion] Within the region of 490 nm~560 nm wavelength, only two specificexcited states (B0 and A(1)) dominantly contribute to the first-rank polarization parameter.
Hence the first-rank polarization parameter can be written as:Im [a1(1 ) (ٛ// , ⊥ )] ∝ f (X → B → B ) f (X → A → A )sin (ĳ + − ĳ A(1) ) 㸬
B0

The parameter represents the orientation of the angular momentum ofphotofragment Cl (2P3/2) in a recoil direction of 45 degrees from lightpolarization vector. f (X → B → B)  for the // component represents
the vertically excited wavepacket which has the contribution of TDM
from the X0+ state, and propagates adiabatically on the B0+ state up
to the asymptotic limit (see Fig. 1). In a similar manner,f (X → A → A )  IRU the ԋ component represents the contribution
from the Franck-Condon wavepacket on the A(1) state, which
dissociates adiabatically on the same state. The phase part in eq. (1) )LJ&RUUHODWLRQVFKHPH
is the phase difference of the de Broglie waves on the
RI HOHFWURQLF VWDWHV LQ WKH
B0+ and A(1) states at the dissociation limit. Since the
SKRWRGLVVRFLDWLRQSURFHVVde Broglie waves depend critically on the available
energy, PEC, and NACT, a strong wavelength
dependence of the parameter in general agreementwith experiment (Fig. 2), implies a high accuracy of
the PECs.
[1] A. J. Alexander and T. P. Rakitzis, Mol. Phys. 103.
1665 (2005)
)LJ  )LUVW UDQN SDUDPHWHU &LUFOHV([SW>@%OXHFXUYHWKLVZRUN

313

3PP-65

Quantum modeling the cooperative laser electron-γ-nuclear
effects in spectra of molecular systems
Alexander Glushkov,1,2 Svetlana Malinovskaya,1 Andrei Svinarenko1
1
Odessa OSENU University, P.O.Box 24a, Odessa-9, 65009, Ukraine
2
ISAN, Russian Academy of Scinces, Troitsk, Moscow reg., 142090, Russia
A new class of problems has been arisen in the modern quantum optics and spectroscopy
and connected with modelling of the co-operative laser-electron-nuclear phenomena in
the atomic and molecular systems [1]. It includes a calculation of the probabilities andenergies of the mixed γ-optical quantum transitions in molecules, intensities of thecomplicated γ-transitions due to the changing of the molecular excited states population
under action of laser radiation, quantum calculation of the “laser-nuclear-molecule”
systems [2]. Due to the emission or adsorption of the nuclear γ-quantum in molecularsystem there is changing the electron vibration-rotation molecular states. We developed
new quantum approach to calculation of electron-nuclear γ transition spectra (set ofvibration satellites) of nucleus in a molecule, based on relativistic density functional(DF) formalism and energy approach (S-matrix formalism of Gell-Mann and Low) [1].
Decay and excitation probability are linked with imaginary part of the atom ( molecule) field system. Calculation results of electron-nuclear γ-transition spectra of the nucleus insome atomic, multiatomic systems are given. As illustration in fig.1a.b spectrum ofemission and adsorption of nucleus 127I (Eγ=203keV) in molecule of H127I is presented(the initial state of molecule: (a) va=0,Ja=0; b). νa=1, Ja=0). Estimates are made forvibration-nuclear transition probabilities for number of molecules: diatomics, 3-atomic
XY2 (D∝h), 4-atomic XY3(D3h), 5-atomic XY4(Td), 7-atomic XY6(Oh) ones.

ab[1] A.Glushkov, O.Khetselius, S.Malinovskaya, Europ.Phys.J. 2008, 160. 195-204;
Molec.Phys. 2008, 108, 1257; Int.J.Quant. Chem.2004, 99, 889-896; 2005, 104, 496-500;
Frontiers in Quantum Systems in Chemistry and Physics (Springer). 2008, 18, 523-540.
[2] V.I.Gol’dansky, V.S.Letokhov, JETP-Soviet Phys. 1974, 78, 213-216; L.N.Ivanov,
V.S.Letokhov, ibid, 1987,93,396-404; A.V.Glushkov, L.N.Ivanov, Phys.Lett.A 1992,
170, 33-38.

314

3PP-66

Raman scattering of the light on metastable levels of diatomics
with an account for nuclear motion contribution
Alexander Glushkov,1,2 Olga Yu. Khetselius,1 and Andrei Svinarenko1
1
Odessa OSENU University, P.O.Box 24a, Odessa-9, 65009, Ukraine
2
ISAN, Russian Academy of Scinces, Troitsk, Moscow reg., 142090, Russia
Laser action on molecules leads to different non-linear processes, including themulti-photon ionization, excitation and dissociation, Raman scattering. The elementary
two-photon processes are a linear coherent and a combinational scattering. The intensities
and polarization of lines in these spectra are defined by polarizability and derivative oninter-nuclear distance. In this paper it is considered a process of Relay and Raman
vibration scattering of the light on metastable levels of molecules (H2, HD, D2, Li2, Rb2,
Cs2). On the example of polarizability of metastable molecules it has been studied aneffect of nuclear motion in processes of the second order of the perturbation theory [1].
New numerical method for construction of the Green electron functions for opticalelectrons and electron wave functions is developed within the pseudo-potential approachin the spheroid coordinates system that allows to take into account non-sphericalcharacter of molecular field.
We present the results of calculation of the molecular polarizability, its derivativeon the inter-nuclear distance, a depolarization degree under Relay and Raman lightscattering on the frequencies of the Rb, Nd lasers. Analysis of results of the calculation ofa polarizability, its derivative on inter-nuclear distance, for example, for excited triple
metastable c3Πn, states of the H2, HD, D2 molecules on the frequencies of the Rb (1,78eV)
and Nd (1,18eV) lasers shows that the main contribution into the polarization of the citedmetastable molecules is provided by changing the electron shell under action of theexternal electromagnetic field. An influence of the nuclear motion terms is in details
considered too.
We have presented a relativistic generalization of the approach too. It is based onusing the generalized dynamical nuclear model and the relativistic perturbation theory
with account of the exchange-correlation effects [1].
[1] A.V. Glushkov, Rus. J. Struct. Chem. 1990, 31, 9; 1992, 32, 11; 1993, 34, 3; Rus. J.
Phys.Chem. 1992,66, 589; 1992, 66, 1259; Int. Journ. of Quant.Chem. 2005, 104, 562;
J. Phys.CS. 2006, 35, 420.
[2] A.V.Glushkov, L.N.Ivanov, Phys.Lett.A 1992, 170, 33; A.V.Glushkov, O.Khetselius,
S.V.Malinovskaya, Molec.Phys. 2008, 108, 1257; in Frontiers in Quantum Systems in
Chemistry and Physics, Progress in Theoretical Chemistry and Physics, ed. by S.
Wilson, P.J. Grout., J. Maruani, G. Delgado-Barrio, P. Piecuch (Springer, Berlin) 2008,
18, 505.

315

3PP-67

Electric Field Can Induce Heterogeneous Ice Nucleation
J. Yan and G. N. Patey

Abstract
Molecular dynamics simulations of confined water were carried out to study heterogeneous ice
nucleation induced by an electric field under the freezing point. A very simple model, with anelectric field that acts only within a very short distance of a surface was examined. We
demonstrate that with this arrangement, ice nucleates readily at the surface, and grows outwardly
into the bulk. It is found that proton disordered cubic ice, has grown onto the proton orderedferroelectric layer, in a near seamless manner.

316

3PP-68

First Principles investigations on lithium – graphite interactions
1

Alain Allouche
PIIM, CNRS & Université de Provence, Marseille, France

The interaction of a lithium atom and a graphitic surface has many interests inmany domains of energy production:
1) The future tokamak ITER aims to demonstrate that the nuclear fusion of
deuterium and tritium nuclei is an energy source of the future. Unfortunately the highly
energetic D/T plasma confined in this device seriously damages the materials cladding
the inner walls of the tokamak, and this an essential issue for the ITER feasibility.
Deposition of a lithium thin layer onto the graphitic elements was found to considerably
decrease the carbonaceous materials erosion.
2) Hydrogen storage has been identified as a major challenge in theimplementation of hydrogen as a fuel in vehicles. Graphite based materials are the mostoften proposed candidates for this purpose, and lithium strongly increases the H storage
capacity.
3) Diffusion on and into the graphite surface precedes the formation of lithium –graphite intercalation compounds which can replace lithium metal electrodes inrechargeable Li-ion batteries.
From a quantum point of view, the lithium - graphite interaction can be atomic orionic according to the situation. This contribution details DFT studies on themechanisms of a single lithium atom interaction with the pristine or defective (0001)
graphite surface. Because the Li(2s) energy level is so close to the graphite Fermi
energy, there is a very subtle competition between hydrogen atom adsorption on carbon
or Li atoms. Co-adsorbed atomic oxygen or atomic vacancies can displace thiscompetition in one direction or the other.
We will also study the effects of lithiation and oxidation of graphite on of atomic
hydrogen storage.

317

3PP-69

Computational studies of viral influenza A neuraminidase subtype N1
Thanyada Rungrotmongkol,1,2 Supot Hannongbua1,21Computational Chemistry Unit Cell, Department of Chemistry, Faculty of Science,
Chulalongkorn University, Thailand
2

Center of Innovative Nanotechnology, Chulalongkorn University, Thailand

While the seasonal influenza viruses spreading around the world cause the annual
epidemics, the recent outbreaks of influenza A virus subtypes H5N1 and pandemic
H1N1 (pH1N1) have raised a global human health concerns. We aimed at gaining
insight into molecular details at neuraminidase (NA) of these two viruses. Interest is
focused on drug’s inhibitory activity against the wild-type and mutated N1 strains.
Based on molecular dynamics approach in couple with linear interaction energy method,
the pH1N1 NA was predicted to be susceptible to oseltamivir, with all importantinteractions being well conserved [1]. For both viruses [2,3], the known H274Y
mutation conferred the high oseltamivir-resistance with decreased hydrophobicity,
pocket size and vdW interactions at the bulky group. Instead, N294S was found todemonstrate medium drug-resistant level. Investigation was also extended to
combinatorial chemistry drug design of NA inhibitors using the oseltamivir andpyrrolidine scaffolds [4,5]. From the large diversity combinatorial library, the small
highly focused combinatorial subset of both designed analogs was proposed to contain
NA inhibitors with considerably higher potencies toward the N1 enzyme than their parent
inhibitors, oseltamivir and A-315675. A better understanding of molecular inhibition andsource of drug resistance as well as a set of newly designed compounds is greatly usefulas a rotational guide for synthetic and medicinal chemists to develop a new generation ofanti-influenza drugs.
[1] T. Rungrotmongkol, P. Intharathep, M. Malaisree, N. Nunthaboot, N. Kaiyawet, P.
Sompornpisut, S. Payungporn, Y. Poovorawan, S. Hannongbua, Biochem. Biophys. Res.
Commun. 2009; 385(3):390-394.
[2] T. Rungrotmongkol, T. Udommaneethanakit, M. Malaisree, N. Nunthaboot, P.
Intharathep, P. Sompornpisut, S. Hannongbua, Biophys. Chem. 2009; 145(1):29–36.
[3] T. Rungrotmongkol, M. Malaisree, N. Nunthaboot, P. Sompornpisut, S. Hannongbua,
Amino Acids 2010; 39(2):393-398.
[4] T. Rungrotmongkol, V. Frecer, W. De-Eknamkul, S. Hannongbua, and S. Miertus,
Antiviral Res. 2009; 82(1):51-8.
[5] T. Rungrotmongkol, T. Udommaneethanakit, V. Frecer, S. Miertus, Comb. Chem.
High Throughput Screen. 2010; 13(3):268-77.

318

3PP-70

Linearly conjugated chains exposed to an electric ﬁeld: A closer look on
the polarizabilities obtained with several quantum chemical methods
Peter A. Limacher,1,2 Hans P. Lüthi,1 Paul W. Ayers2
1
Laboratory of Physical Chemistry, ETH Zürich, Switzerland
2
Department of Chemistry, McMaster University, Canada

Second Hyperpolarizability γ / a. u.

Conjugated molecular chains such as polyacetylene (alternating double and single
bonds) or polyyne (alternating triple and single bonds) are materials of considerable
interest to the chemical industry and material sciences as they exhibit large nonlinear
optical eﬀects when exposed to electric ﬁelds.
Unfortunately, the quantum chemical description of these systems, and in particular the calculation of polarizabilities and hyperpolarizabilities, is by no means
trivial. It is well known, that conventional DFT fails to predict accurate values
for these properties due to limitations in the exchange functional.[1] Especially forextended chains, this leads to a tremendous overestimation of the polarizabilities
along the molecular propagation axis. The inclusion of pure HF-exchange in the
recently developed longrange-corrected density functionals however, was successful
in predicting more meaningful polarizabilities.[2][3]1.5e+08

X

Y

n

1e+08

CCSD
HF
SVWN
BLYP
B3LYP
LC-BLYP
CAM-B3LYP

5e+07

0
2

4

8
6
Number of double bonds n

10

12

In the meantime, it has been noted that also electron correlation has an unexpected eﬀect on the polarizabilities of these systems: The initially positive contribution of electron correlation to the second hyperpolarizability of small systems isconstantly diminishing when the chain length is extended and can even turn into a
negative contribution for suﬃciently large systems.[4][5][1] S.J.A. van Gisbergen, P.R.T. Schipper, O.V. Gritsenko, E.J. Baerends, J.G. Snijders, B. Champagne, and B. Kirtman, Phys. Rev. Lett. 83, 694 (1999).
[2] H. Sekino, Y. Maeda, M. Kamiya, and K. Hirao, J. Chem. Phys. 126, 014107 (2007).
[3] P.A. Limacher, K.V. Mikkelsen, and H.P. Lüthi, J. Chem. Phys. 130, 194114 (2009).
[4] Q. Li, L. Chen, Q. Li, and Z. Shuai, Chem. Phys. Lett. 457, 276 (2008).
[5] P.A. Limacher, Q. Li, and H.P. Lüthi, J. Chem. Phys., in press.

319

3PP-71

Molecular modeling of silver adsorption on Į-quartz surface
N.I.Vakula1, G.M. Kuramshina1
1Faculty of Chemistry, Moscow State University (M.V.Lomonosov), Moscow, 119991, Russia

Metal island films (MIFs) have many interesting properties and, particularly, a unique opticalbehavior. These films are effectively used as selective absorbers, optical polarizers, and data
storage, etc. Using the optical behavior of MIFs opens up the possibility to produce low-cost
photonic heterostructures.
In the present study, the new results on determining the suitable locations for incorporation ofsilver adatoms on the silica (001) surface has been performed. A series of searches has been
carried out and all possible configurations have been optimized within first-principle calculations(DFT and QM/MM) with a goal to investigate the electronic structure and adsorption energy ofsilver atoms deposited on the silica (001) surface. An orthorhombic supercell with a slab of Įquartz has been used for modelling (001) surfaces (Fig.1). The initial configuration of thecompletely hydroxylated surface has been obtained by saturating the terminal oxygen atoms on
both the top and bottom surfaces by hydrogen atoms.

ab

Figure 1. Side view (a) and top view (b) of silica (001) surface used in calculations
All calculations have been performed with CP2K code1. The technique based on the Quickstep2
implementation of the density functional theory (DFT) method with Gaussian and plane waves(GPW3) scheme has been utilized. We have used the generalized gradient functional PBE and theGoedecker-Teter-Hutter4 pseudopotentials in conjunction with TZVP basis sets.
Acknowledgement. We thank Research Computing Center, M.V. Lomonosov Moscow State
University for the facilities and the use of SKIF MSU "Chebyshev" Supercomputer. This work
was partially supported by the RFBR grant No 011-03-00040a.
1

Kohlmeyer. A.; Mundy. C. J.; Mohamed. F.; Schiffmann. F.; Tabacchi. G.; Forbert. H.; Kuo. W.; Hutter.

J.; Krack. M.; Iannuzzi. M.; McGrath. M.; Guidon. M.; Kuehne. T. D.; Laino. T.; VandeVondele. J.;
Weber. V. CP2K, 2004, http://cp2k.berlios.de2

VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J. Comput. Phys.
Commun. 2005, 167, 103–128.
3

Lippert, G.; Hutter, J.; Parrinello, M. Mol. Phys. 1997, 92, 477–487.

4

Goedecker, S.; Teter, M.; Hutter, J. Phys. ReV. B 1996, 54, 1703–1710.
320

3PP-72

Theoretical study of [2+2] cycloaddition of cyclopentyne and ehtylene:
Multireference and broken-symmetry approach
Toru Saito,1 Yasutaka Kitagawa,1 Mitsutaka Okumura,1 Kizashi Yamaguchi2
1
Department of Chemistry, Graduate School of Science, Osaka University, Japan
2
Center for Nanomaterial Design, Osaka University, Japan
Abstract
The [2+2] cycloaddition reaction of cyclopentyne and ethylene is examined byboth the multireference (MR) and spin-unrestricted Hartree-Fock (UHF) based coupled cluster (CC) calculations. We focus on the competition between diradical stepwise and concerted mechanisms in the reaction. We have demonstrated that the spin
contamination eﬀect caused by the triplet state still remains at the UHF-CCSD(T)level [2-5]. To remove the spin contamination eﬀect, an approximate spin-projection(AP) method is applied to the singlet solutions. The CC with the spin-unrestricted
Brueckner determinant (UBD(T)) calculations were also performed because UHFCCSD poorly describes the π conjugated organic species [6-8]. At the transition
state, the calculated S2  values for the singlet solutions are ∼ 0.7 and ∼ 0.1 obtained by UCCSD(T) and UBD(T), respectively, supporting that UBD(T) significantly suppresses the diradical character. Comparison of the activation barrierheights including thermal corrections between two mechanisms suggests that they
are competitive and the diﬀerence is within 0.5 kcal/mol. The present results are
consistent with the CR-CCSD(T) results of Kinal and Piecuch [9]. On the other
hand, the stepwise pathway is favorable than the concerted pathway by 2.0 kcal/mol
at the MkMRCCSD/cc-pVDZ level.
[1] L. Fitjer et al. Tetrahedron Lett. 23, 1661 (1982).
[2] T. Saito et al. Chem. Phys. Lett. 483, 168 (2009).
[3] T. Saito et al. J. Phys. Chem. A 114, 7967 (2010).
[4] T. Saito et al. J. Phys. Chem. A 114, 12116 (2010).
[5] T. Saito et al. Theor. Chem. Acc., in press.
[6] T. Saito et al. Chem. Phys. Lett. 498, 253 (2010).
[7] T. Saito et al. Mol. Phys. 108, 2533 (2010).
[8] T. Saito et al. Theor. Chem. Acc., in press.
[9] A. Kinal, P. Piecuch, J. Phys. Chem. A 110, 367 (2006).

321

3PP-73        * $,) !)!
                )0*+##!% &)&% /!*+* * *-)# '&#0$&)' * $&% + $ +  3++)&%#&)&% ++)+* ++%+!&% )&$ )*) )* , +& !+**+),+,)# ,%!(,%**+ +!*++) )#))%$%+&!&* )**%!%+ &##&.!%!,) %!+!&%+&&,)!&* )+.&!%+)*+!+!# &)&%  +&$* )!%*)+ %+  !*+&)0&&)&%)*)  +  3++)&%# ' * * % &,'0!%  *'!# '&*!+!&% +& *  + %+,)&+ !&* )#&%!% %!+!##0!+.*+ &, ++ ++ )0*+#!*&$'&*
%+.&!%+)*+!+!# +&$*!%  +&$*!%+ ##&.-)*+ &&,)
*+),+,)#)!%$%+.*')&)**!+$#)+ +',)  *+),+,)#&%.*,%*+#$',)!+!**, *&)+&$*)!%&)'&)+!%+  )0*+# %&%#0!%+ !*&)$ 3++)&%# ' *%*+!#!1 )%+*,)')!*!*+ +!%*'!+&+ !*$+*+# +,) ',)  &)$ !* )'&)+ !% %%&*+),+,) &)&% *,  *%%&)!&% &) %%&#+  ) !* %& &%*%*,* ))!% +  *+!#!+0 & 3++)&%#' * !% %%&*+),+,)* % + !* .&)" . !%-*+!+ +  &)$+!&% & 3++)&%#' * % +  #+)&%! *+),+,) 0 !)*+')!%!'#* '*,&'&+%+!# $+ & &) ,#")0*+#   %+ #'0 & &)$+!&% 2 & -)!&,* +* .!+  )*'+ +& ',) 3++)&%# ' * )-# + + +  ',)* &$$&%#0 *+),+,) !* ,%*+#&*)-!%&+ )&)&%)0*+#*+ !%+)!&* )&%#%+ *)* &)+)+ %+ !%+)!&* )&%#%+ *+$%* + ++ !%+)*+!+!#*!+*'#0),!#)&#&%+ *+!#!+0&)0*+#  &%&% #,#+!&% &+  3++)&%#&)&%&%!)$+ *+)&%
&%!% +.% +.& !&* ) ,%!+*  &*)- +   )+)!*+! ' %&$%&%
. % +  &)!% +&$* ) !%&)'&)+ !% + !* *+),+,)    ' &%&% *'+),$* &. +  !%+) !&* ) &% *+)%+  % % 0 +  &)!% +&$* #!"  
%    
&))*'&%!%,+ &)322

  

3PP-74

Packing effects in organic donor-acceptor molecular heterojunctions
Mikiya Fujii, Koichi Yamashita
Department of Chemical System Engineering, The University of Tokyo, Tokyo 113-8656,
Japan
I. Introduction
Organic semiconductors have been widely investigated for photovoltaic and lightemitting devices. Especially, further improvements of more efficient organic solar cells(OSCs) are desired. Thus, we explored possibilities to make OSCs more efficient by
adjusting the packing of molecular heterojunctions.
II. Computational methods
We
analyzedamolecular
heterojunction
that
consistsofpoly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylenediamine)
(TFB)
and
poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT). Geometrical optimization of
TFB(monomer)/F8BT(monomer) complex was carried out with DFT-D/B3LYP/6-31G*.
Excited states were also calculated with CIS/6-31G*. To analyze packing effects incharge transfer dynamics from TFB to F8BT, we rotated TFB around a principal axis.
Then, we analyzed the charge transfer with a quantum master equation (QME)
approach.
III. Results
A stable structure is shown in Fig. 1. From the excited states calculations, it isclarified that the packing strongly affects the energy level of the charge transfer state
only (Fig.2). This packing dependency arises from a packing dependency of the exciton
binding energy that is Coulomb interaction between an electron localized to F8BT and ahole localized to TFB. From the QME approach, it is confirmed that qualitative different
electronic relaxation dynamics occurs in each different packing. Therefore, we conclude
that the packing that is suitable for photovoltaic devices and the packing that is suitable
for light emitting devices are different.
(a)

(b)

Fig1. A stable structure and molecular orbitals
of TFB/F8BT complex. Upper and Lower
molecules are F8BT and TFB, respectively.
(a):HOMO. (b)LUMO

323

Fig. 2 Packing dependency of theexcited states.

3PP-75

Theoretical Study of Interaction between Gas Molecule andPaddle-Wheel Unit of MOF
Yuh Hijikata, Shigeyoshi Sakaki*
Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, Japan
I. Introduction
Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs), which
are constructed from organic linkers and metal ions, have attracted a lot of interests intheir excellent abilities for gas storage and separation. Some of PCPs possess open
metal sites (OMSs) which work as interaction sites for gas molecules. The paddle wheel
unit is one of good examples, which is often used as building unit for many PCPs. We
theoretically investigated the interaction energies (Eb) of several molecules with thepaddle wheel unit, their bonding nature, and change of electronic structure.
II. Computational detail
In the paddle wheel unit, two metal ions are connected byorganic linkers. The axial positions are OMSs, as shown Scheme 1.
Structures were optimized by DFT method with M06L functional. Eb
was evaluated with MP2 to MP4(SDTQ). In M=Cu, the difference of
Eb between triplet and open shell singlet states were considered as
Scheme 1.
shown in Scheme 2, while in M=Ni, singlet, triplet, and quintet state
were investigated.
III. Results and discussion
The difference of Eb between open shell singlet
and triplet spin states was negligibly small in M=Cu.
This is because L mainly interacts with Cu 4pz orbital,
Scheme 2.
while Cu dx2-y2 orbital little participates in theinteraction with L. As listed in Table 1, Eb increases in the order NO ~ N2 < CO <<CH3CN < CH3NC. This trend agrees with the trend of the charge transfer from L to Cu,
except for CH3CN and CO. This exceptional result is interpreted in terms of thenegatively charged N of CH3CN and positively charged C of CO. In Ni(II) complexes,
the interaction of gas molecule induces change of spin multiplicity from triplet toquintet, interestingly. The change of spin state and comparison of Eb between Ni and Cu
will be presented in the poster.
Table 1. Eb values of various gas molecules with the Cu(II) paddle-wheel complex intriplet state (R=H).
L
CO
CH3CN
CH3NC
NO
N2
-1 a)
Eb / kcalmol
6.5
12.5
14.9
4.0
4.1
r(Cu-L)
2.267
2.193
2.174
2.292
2.394
Charge transfer from L
0.213
0.125
0.222
-0.111
0.100
a)

The stabilization energy per one gas molecule. The MP2 method was employed. Counterpoise correction was made.

324

3PP-76

Electronic structures and molecular structures of polyynes
Akira Imamura,1 Yuriko Aoki2,3
1
Faculty of Engineering, Hiroshima Kokusai Gakuin University, Japan
2
Faculty of Engineering Sciences, Kyushu University, Japan
3
Group PRESTO, Japan Science and Technology Agency, Japan
I. Introduction
Recently, many interesting materials made from carbon atoms have been discovered
such as carbon nanotubes, fullerenes and graphenes. In this paper, we studied electronic
structures and molecular structure of polyynes with sp2 carbons on both ends.
II. Molecules and method of calculations
Polyynes calculated were H2CCnCH2 with various number of n. These molecules
have two ʌ systems which are perpendicular to each other and these ʌ systems havetheir tendency to make double bond nature by Peierls instability but for different
alternating bonds. In other words, these two ʌ systems are competing to form the doublebond formations. The calculations were carried out with Gaussian 03 with geometry
optimization in 6-31G and 3-21G basis sets.
III. Results and Discussion
For CH2(C)38CH2 and CH2(C)48CH2 , there have been found two metastablestructures, one of which is the bond-alternating structure and another is nearlyequi-bond structure. The former has small HOMO-LUMO gap while the latter has therelatively large gap although it is smaller in comparison with the value of polyyne with
sp carbon atoms on both ends such as H(C)40H and H(C)50H. The small HOMO-LUMO
gap in bond-alternating structure is due to the fact that HOMO and MO’s near to
HOMO have relatively localized electronic distribution in both end regions and thus the
weak interaction between the both regions leads to the small HOMO-LUMO gap. The
stability is larger for the former especially in long polyynes. The calculated numericalvalues are listed in Table I. This result can be explained by using the perturbation theory
published previously[1]. We will describe in detail at the poster session.
Table I. HOMO-LUMO gap and total energy of polyynes with 6-31G (energy in a.u.)molecule
structure
HOMO
LUMO
gap
Tot. Energy
H2C(C)38CH2 Bond-alter-0.1450-0.13140.0135-1515.2609
H2C(C)38CH2 Equi-bond-0.2410-0.05810.1829-1515.2101
H2C(C)48CH2 Bond-alter-0.1434-0.1333
0.0101-1893.5445
H2C(C)48CH2 Equi-bond-0.2389-0.06200.1769-1893.4261
IV. Conclusion
Interesting relationship between electronic structures and molecular structures ofpolyynes are found and discussed.
[1] Y.Aoki and A.Imamura, J. Chem. Phys., 103, 9726-9737(1995).

325

3PP-77

Structural dependence of the open-shell characters and second
hyperpolarizabilities in one-dimensional systems composed oftrigonal graphene nanoflake units
Kyohei Yoneda,1 Hitoshi Fukui,1 Takuya Minami,1 Yasuteru Shigeta,1
Takashi Kubo,2 Edith Botek,3 Benoît Champagne,3 Masayoshi Nakano1
1
Graduate School of Engineering Science, Osaka University, Japan
2
Graduate School of Science, Osaka University, Japan
3
Facultés Universitaires Notre-Dame de la Paix, Belgium

4

γ [x10 a.u.]

I. Introduction
In our previous studies, we have theoretically found that the second
hyerpolarizability (γ) [the microscopic origin of the third-order nonlinear optical (NLO)
property] for open-shell singlet molecules shows a remarkable open-shell character
dependence: the systems having intermediate open-shell characters tend to exhibit alarge enhancement of γ as compared to the closed-shell andpure open-shell systems [1]. We have studied graphene
nanoflakes (GNFs) with several sizes and architectures as
AL system
promising candidates of open-shell singlet NLO systems [2].
In this study, we investigate the structural dependence of
NAL system
the open-shell characters as well as of the γ values forseveral one-dimensional systems composed of the smallest Fig. 1. 1D systems composedof trigonal GNF units
trigonal GNF units (Fig. 1) [3].
II. Results and discussion
These systems show a wide range of open-shell
14000
AL systems
12000
characters, strongly depending on the linked form of
NAL systems
10000
trigonal GNF units, which is useful for controlling γ.
8000
In particular, in singlet alternately linked (AL) systems,
6000
having intermediate multiradical characters, γ is larger
4000
and increase supralinearly with the number of units (N)2000
faster than in the non-alternately linked (NAL) systems,
0
2
4
6
8
10
having a pure multiradical character (Fig. 2). TheseN [-]features provide a novel guideline for the molecularFig. 2. The γ values of AL and
NAL systems
design of GNF based NLO materials.
[1] M. Nakano et al., J. Phys. Chem. A 109, 885 (2005); Phys. Rev. Lett., 99, 033001(2007). [2] M. Nakano et al., Chem. Phys. Lett. 467, 120 (2008); K. Yoneda et al.,Chem. Phys. Lett. 480, 278 (2009); H. Nagai et al., Chem. Phys. Lett. 489, 212 (2010).
[3] K. Yoneda et al., ChemPhysChem. 12, 1697 (2011).

326

3PP-78

An efficient light-harvesting system to excite
optically-forbidden states of molecular aggregates
Go Tei, Masatoshi Nakatani, and Hajime Ishihara
Graduate School of Engineering, Osaka Prefecture University, Japan
I. Introduction
Two types of ring-shaped pigment-protein complex, peripheral light harvesting
complex (LH2) and core light-harvesting complex (LH1) are involved in thephotosynthetic light-harvesting process of photosynthetic bacteria. The energy ofsunlight absorbed by LH2 efficiently migrates to LH1, where the photosynthetic
reaction center is located at the center of LH1. It is pointed that the geometricalstructure of LH2, the characteristic ring shape, could positively function to achieve highefficient energy transfer in photosynthetic systems [1, 2]. On the other hand, it is
proposed that, in particular resonant conditions, photon energies received by the metal
structures forming a nano gap serving as an artificial light harvesting antenna can beconcentrated into the target molecules in the vicinity of the nano gap without a large
dissipation in the metals [3]. By employing a simple model, we show that such energy
transparency can also occur between the optically allowed states of an antenna ring andthe optically-forbidden states of a target ring, where antenna and target ring are theaggregate of point dipoles imitating the geometrical structure of LH2 and LH1,
respectively.
II. Model and Results
We consider a model system consisting of target and antenna rings, which aremodeled as the aggregate of point dipoles imitating the geometrical structure of LH1and LH2, respectively. To investigate the population dynamics in the system, a method
based on the nonlocal response theory and a Markovian quantum master equation is
employed, which enables us to treat electric field and polarization of point dipoles selfconsistently. We found that, in particular resonant conditions, photon energies received
by the optically-allowed states of the antenna ring can be concentrated into theoptically-forbidden states of the target ring efficiently suppressing the relaxation in theantenna ring. It could be an example of efficient light-harvesting system to excite
optically-forbidden states of molecular aggregates.
[1] G. Tei et al, Physica Status Solidi (b), 248, 399 (2010)[2] M. Nakatani et al, Physica Status Solidi (b), 248, 448 (2010)[3] H. Ishihara et al., J. Photochem. Photobio. A (2011) in press327

3PP-79

Theoretical Study on Electronic Structures of
μ-oxo-Bridged Manganese Complex
Nanami Seki,1 Akira Nakayama,2 and Tetsuya Taketsugu2
1
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Japan
2
Graduate School of Science, Hokkaido University, JapanThe manganese complex has received much attention
both theoretically and experimentally since manganese shows
particularly rich redox property with several oxidizing states.
In particular, the oxygen-evolving complex (OEC) inphotosystem II (PSII), which is composed of a μ-oxo-bridged
tetra-nuclear manganese cluster (Fig. 1), is known to oxidize
water molecules into oxygen molecules efficiently [1], and its
imitative complex (Fig. 2) also has the ability to evolve
oxygen [2], so there is a growing interest in utilizing this kindof manganese complex as a catalyst in water splitting. In
most theoretical studies on this type of metal complexes,
density functional theory (DFT) methods have been
employed to predict the structural and electronic properties
and to investigate the reaction mechanism, with a reasonable
cost. As to the relative energies of different spin states with
open-shells of d-electrons, however, DFT methods are notconsidered to predict an accurate result [3].

Figure 1. PSII
oxygen-evolving
complex (OEC)In this work, we applied multi-configurational
Figure 2. OEC
self-consistent field (MCSCF) method, as well as B3LYP
imitative complex(DFT) method, with Sapporo-DZP basis sets [4], to
Mn2O2(tpy)2(H2O)2
investigate the electronic structures of the highest/lowest spinstates of several kinds of di-μ-oxo-bridged manganese dinuclear complex and to
estimate the effective exchange integrals value (J) in detail, and discuss about thecapabilities of the DFT method. In DFT calculations, the low-spin states arecalculated by the broken-symmetry technique. More details and discussions are given in
the poster session.
References[1] V.K. Yachandra, K. Sauer, and M.P. Klein, Chem. Rev. 96, 2927 (1996).
[2] J. Limburg, J.S. Vrettos, L.M. Liable-Sands, A.L. Rheingold, R.H. Crabtree,
and G.W. Brudvig, Science 283, 1524 (1999).
[3] E.M. Sproviero, J.A. Gascon, J.P. McEvoy, G.W. Brudvig, and V.S. Batista,
J. Inorg. Biochem. 100,786 (2006).
[4] http://www.sci.hokudai.ac.jp/sapporo/328