Supporting Information for ”Electron-vibron coupling in halogenated…“ by N. Schmidt et al.
Supporting Information
“Electron-vibron coupling in halogenated acenapthenequinone
upon O K-edge soft X-ray absorption”
by Norman Schmidt, Tim Clark, Stephen G. Urquhart, and Rainer H. Fink
Supporting Information for ”Electron-vibron coupling in halogenated…“ by N. Schmidt et al.
Additional density-functional theory (DFT) calculations were performed to investigate the
electron density in the ground-state HOMO and LUMO of both ANQ and Br2Cl2-ANQ. All
calculations used the Becke 3-parameter functional (B3LYP)1 as implemented in
GAUSSIAN09.2 Geometries were optimized without symmetry constraints. The orbital plots
shown in Fig. 1 were calculated using DMOL3 3–6 with the PW91 functional and the DNP basis
set3–6 within MATERIALS STUDIO 5.0.7
Figure S1: Electron density distributions for the HOMO (bottom) and LUMO (top) of ANQ
(left) and Br2Cl2-ANQ (right) as derived from PW91/DNP calculations using DMOL3 and
visualized with MATERIALS STUDIO 5.0.
Fig. S1 shows the electron density of the HOMOs and LUMOs of the investigated
acenaphthenequinones in the ground state. The electron density of the HOMO is mainly
located on the carbonyl functions. The LUMO corresponds to the MO into which the O 1s
core electron is excited. The density is also located on the carbonyl groups but with a different
nodal structure compared to the HOMO. Of course, the calculated LUMO neglects the effects
Supporting Information for ”Electron-vibron coupling in halogenated…“ by N. Schmidt et al.
of core hole localization and symmetry reduction upon core excitation. Nonetheless, the
LUMO resembles some features of the SOMO (Fig. 4 in the paper). The LUMO shows, like
the SOMO, antibonding character along both carbonyl bonds and bonding character for the CC bond between the carbonyl C atoms. The LUMO also shows no involvement of the C-H
bonds. On the other hand, a discussion based on the ground-state LUMO would underestimate
the role of the halogen atoms, which have a larger coefficient in the SOMO. An increased
bond polarization by the core hole may play a role here.
A. D. Becke, J. Chem. Phys. 1993, 98, 5648–5652.
GAUSSIAN09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P.
Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F.
Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E.
Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, Y. Yazyev, A. J. Austin, R.
Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox,
Gaussian, Inc., Wallingford CT, 2009.
B. Delley, J. Chem. Phys. 1990, 92, 508–517.
B. Delley, J. Chem. Phys. 1991, 94, 7245–7250.
B. Delley, J. Phys. Chem. 1996, 100, 6107–6110.
B. Delley, J. Chem. Phys. 2000, 113, 7756–7764.
MATERIALS STUDIO 5.0, Accelrys Inc., San Diego, 2010.