# Double core-hole states in SiX4 (X = F, Cl, Br, and CH3) molecules derived by photoelectron and KLL Auger spectroscopy

R Püttner, T Marchenko, R Guillemin, L Journel, G Goldsztejn, J-P Rueff, D

Céolin, D W Lindle, A Lago, K Ueda, et al.

► To cite this version:

R Püttner, T Marchenko, R Guillemin, L Journel, G Goldsztejn, et al.. Double core-hole states in SiX4 (X = F, Cl, Br, and CH3) molecules derived by photoelectron and KLL Auger spectroscopy. Journal of Physics: Conference Series, 2015, 635 (11), pp.112057-112057 hal-01266846

HAL Id: hal-01266846

https://hal.sorbonne-universite.fr/hal-01266846

Submitted on 4 Feb 2016

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
Double core-hole states in SiX₄ (X = F, Cl, Br, and CH₃) molecules derived by photoelectron and KLL Auger spectroscopy

This content has been downloaded from IOPscience. Please scroll down to see the full text.

2015 J. Phys.: Conf. Ser. 635 112057

(http://iopscience.iop.org/1742-6596/635/11/112057)

View the table of contents for this issue, or go to the journal homepage for more

Download details:

IP Address: 134.157.80.136

This content was downloaded on 03/02/2016 at 13:42

Please note that terms and conditions apply.
# Double core-hole states in SiX$_4$ (X = F, Cl, Br, and CH$_3$) molecules derived by photoelectron and KLL Auger spectroscopy

R. Püttner*<fnref n="1" />, T. Marchenko†,§, R. Guillemin†,§, L. Journel†,§, G. Goldsztejn†,§, J.-P. Rueff¶, D. Céolin¶, D. W. Lindel§, A. Lago#, K. Ueda%, O. Takahashi&, M. N. Piancastelli†,§,‡ M. Simon†,§,¶

* Institut für Experimentalphysik, Freie Universität Berlin, Germany

† CNRS, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, France

§ Sorbonne Universités, UPMC Univ Paris 06, UMR 7614, LCPMR, France

¶ Synchrotron SOLEIL, Gif-sur-Yvette, France

§ Department of Chemistry, University of Nevada, Las Vegas, USA

# Centro de Ciências Naturais e Humanas, Universidade Federal do ABC (UFABC), Santo André-SP, Brazil

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

& Department of Chemistry, Hiroshima University, Japan

‡ Department of Physics and Astronomy, Uppsala University, Sweden

**Synopsis** In recent years double core-hole states are intensively studied since their chemical shifts provide detailed information about initial-state and relaxation effects in a molecule. We derived the Si $1s^{-1}$, $2s^{-1}$, and $2p^{-1}$ binding energies as well as the Si $2s^{-2}$, $2s^{-1}2p^{-1}$, and $2p^{-2}$ double-core hole binding energies of different SiX$_4$ systems in order to derive the chemical shifts. Based on these results we created Wagner plots, which give insight in the initial state and the relaxation effects in the different molecules.

In recent years double core-hole states are intensively studied since their chemical shifts provide detailed information about initial-state and relaxation effects in a molecule. Most of these measurements are done either by coincidence spectroscopy and single-photon absorption using synchrotron radiation (e.g. [1]) or by two-photon sequential absorption using free electron lasers as light (e.g. [2]) sources. However, some of these double core-hole states can also be obtained by other means. This holds in particular for $2s^{-2}$, $2s^{-1}2p^{-1}$, and $2p^{-2}$ core-hole states as a result of KLL Auger decay, which can readily be measured using conventional photoelectron spectroscopy.

Using the new experimental setup for high-resolution HAXPES (HArd X-ray PhotoElectron Spectroscopy) in gas phase, which is mounted at the GALAXIES beamline of the synchrotron SOLEIL, we measured the Si KLL Auger spectra of the molecules SiX$_4$ with X = F, Cl, Br, and CH$_3$. Complementary photoelectron spectra of these molecules were recorded in order to derive the Si $1s^{-1}$, $2s^{-1}$, and $2p^{-1}$ single core-hole binding energies. Using these binding energies, the chemical shifts of the Si $2s^{-2}$, $2s^{-1}2p^{-1}$, and $2p^{-2}$ double core-hole binding energies were derived from the Auger spectra. The obtained binding energies are compared with theoretical results [3] revealing good agreement. Moreover, the results were used to create Wagner plots (i.e. plotting single core-hole energies versus double core-hole energies) for the Si $1s$, Si $2s$, and Si $2p$

core hole state, which give a detailed insight in the initial state and relaxation effects [4]. In particular, they show that the various core holes provide similar information. In addition, the Wagner plots reveal that the initial state effects depend only on the electron-accepting (F,Cl,Br) or electron-donating (H,CH$_3$) character of the ligands. Within these groups differences in the ionization energies are due to varying relaxation energies.

Recently it has been shown for argon that the Ar $1s^{-1}2s$, $p^{-1}$ double core-hole shake-up states are accessible with conventional photoelectron spectroscopy [5]. Here, we present similar Si $1s^{-1}2s$, $p^{-1}$ spectra for all SiX$_4$ molecules. In summary, we show that KLL Auger and photoelectron spectroscopy are well suited to derive information about double core-hole states.

## References

[1] P. Linusson et al 2011 *Phys. Rev. A* **83** 022506 and references therein; P. Lablanquie et al 2013 *Phys. Rev. Lett.* **110** 163001 and references therein.

[2] N. Berrah et al 2011 *PNAS* **108** 16912; P. Salen et al 2012 *Phys. Rev. Lett.* **108** 153003, and references therein.

[3] O. Takahasi et al 2011 *Chem. Phys.* **384** 28.

[4] T. D. Thomas 2012 *J. Phys. Chem. A* **116** 3856.

[5] R. Püttner et al 2015 *Phys. Rev. Lett.* **114** 093001.

<figure><img src="image_2.png" /></figure>

<footnote n="1">¹E-mail: puettner@physik.fu-berlin.de</footnote>