Hybrid density-functional theory calculations of near-edge x-ray absorption fine-structure spectra: Applications on benzonitrile in gas phase
- Laboratoire de Chimie Physique, Matiere et Rayonnement, UMR 7614, Universite Pierre et Marie Curie, 11, rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France)
- Department of Physical Sciences, University of Oulu, P. O. Box 3000, FIN-90014, Oulu (Finland)
- Theoretical Chemistry, Royal Institute of Technology, AlbaNova, S-106 91 Stockholm (Sweden)
The experimental N(1s) near-edge x-ray-absorption fine-structure spectrum of the benzonitrile molecule in the gas phase shows well separated double peaks with different vibrational profiles. Hybrid density-functional theory calculations reveal that such a separation is a result of the conjugation effect on the nitrogen 2p orbitals and the double spectral peaks can be assigned as the N(1s)-{pi}* out-of-plane and in-plane resonances. The vibrational profiles have been analyzed using a combined transition state theory and linear coupling model. Each profile consists of two different vibrational progressions corresponding to stretching modes and a broad continuum of bending excited states. The use of transition state theory allows identifying the dynamics of the N 1s core excitation. It is found that upon core excitations the C-N bond of the benzonitrile molecule can go from initial linear to final bent structures through different paths. The calculated spectrum is in excellent agreement with experiment.
- OSTI ID:
- 20650078
- Journal Information:
- Physical Review. A, Vol. 71, Issue 2; Other Information: DOI: 10.1103/PhysRevA.71.022511; (c) 2005 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA); ISSN 1050-2947
- Country of Publication:
- United States
- Language:
- English
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