Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5416950 | Journal of Molecular Structure: THEOCHEM | 2010 | 6 Pages |
Abstract
Calculations of Franck-Condon factors are crucial for interpreting vibronic spectra of molecules and studying nonradiative processes. On the base of the closed form expression of the Franck-Condon integrals between arbitrary multidimensional harmonic oscillators under the Duschinsky mixing effects, a more general algebraic expression for the calculation of the three-dimensional four-mode Franck-Condon factors was derived straightforwardly and applied to study the photoelectron spectrum of D2CO+(Bâ¼2A1). Geometry optimization and harmonic vibrational frequency calculations were performed on the Xâ¼1A1 state of D2CO at B3LYP, QCISD, CCSD and CASSCF levels, and the Bâ¼2A1 state of D2CO+ at CIS, TD-B3LYP, and CASSCF levels. Franck-Condon analyses and spectral simulations were carried out on the D2CO+(Bâ¼2A1)-D2CO(Xâ¼1A1) photoionization process. The spectral simulations of vibrational structures based on the computed Franck-Condon factors are in excellent agreement with the observed spectrum. In addition, the equilibrium geometric parameters of the Bâ¼2A1 state of D2CO+ were obtained in the spectral simulations.
Related Topics
Physical Sciences and Engineering
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Physical and Theoretical Chemistry
Authors
Chunchun Wang, Chengfeng Liu, Yitao Liu, Jun Liang, Zhifeng Cui,