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Hybrid density-functional theory calculations of near-edge x-ray absorption fine-structure spectra: Applications on benzonitrile in gas phase
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2005 (English)In: Physical Review A. Atomic, Molecular, and Optical Physics, ISSN 1050-2947, E-ISSN 1094-1622, Vol. 71, no 2Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2005. Vol. 71, no 2
Keyword [en]
equivalent-cores approximation, electron binding-energies, polyatomic-molecules, photoelectron-spectroscopy, vibrational structure, chemical-shifts, hydrocarbons, ionization, exchange, model
URN: urn:nbn:se:kth:diva-14585DOI: 10.1103/PhysRevA.71.022511ISI: 000227483900057ScopusID: 2-s2.0-33644526280OAI: diva2:332626
QC 20100525Available from: 2010-08-05 Created: 2010-08-05Bibliographically approved

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Luo, Yi
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Theoretical Chemistry
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