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Title: A new method of calculation of Franck-Condon factors which includes allowance for anharmonicity and the Duschinsky effect : simulation of the He I photoelectron spectrum of ClO₂
Authors: Mok, Daniel K. W.
Lee, Edmond P. F.
Chau, Foo-tim
Wang, Dechao
Dyke, John M.
Subjects: Chlorine compounds
Franck-Condon factors
Digital simulation
Potential energy functions
Wave functions
Photoelectron spectra
Vibrational states
Molecular electronic states
Iterative methods
Issue Date: 8-Oct-2000
Publisher: American Institute of Physics
Source: Journal of chemical physics, 8 Oct. 2000, v. 113, no. 4, p.5791-5803.
Abstract: A new method of Franck-Condon (FC) factor calculation for nonlinear polyatomics, which includes anharmonicity and Duschinsky rotation, is reported. Watson's Hamiltonian is employed in this method with multidimensional ab initio potential energy functions. The anharmonic vibrational wave functions are expressed as linear combinations of the products of harmonic oscillator functions. The Duschinsky effect, which arises from the rotation of the normal modes of the two electronic states involved in the electronic transition, is formulated in Cartesian coordinates, as was done previously in an earlier harmonic FC model. This new anharmonic FC method was applied to the simulation of the bands in the He I photoelectron (PE) spectrum of C1O₂. For the first band, the harmonic FC model was shown to be inadequate but the anharmonic FC simulation gave a much-improved agreement with the observed spectrum. (See Article file for details of the abstract.)
Rights: © 2000 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Daniel K. W. Mok et al., J. Chem. Phys. 113, 5791 (2000) and may be found at
Type: Journal/Magazine Article
DOI: 10.1063/1.1290124   
ISSN: 0021-9606
Appears in Collections:ABCT Journal/Magazine Articles

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