Simulation of (A)over-tilde(1)B(1)->(X)over-tilde(1)A(1) CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects

Chau, F. T., Dyke, J. M., Lee, E. P. F. and Mok, D. K. W. (2001) Simulation of (A)over-tilde(1)B(1)->(X)over-tilde(1)A(1) CF2 single vibronic level emissions: Including anharmonic and Duschinsky effects. Journal of Chemical Physics, 115, (13), 5816-5822. (doi:10.1063/1.1398103).


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CASSCF/MRCI/aug-cc-pVQZ(no g) and RCCSD(T)/aug-cc-pVQZ potential energy functions were reported for the (A) over tilde B-1(1) and (X) over tilde (1)A(1) states of CF2, respectively. Vibrational wave functions of the symmetric stretching and bending modes of the two states of CF2 were obtained in variational calculations, employing Watson's Hamiltonian for a nonlinear molecule and anharmonic vibrational wave functions expressed as linear combinations of harmonic basis functions. Franck-Condon factors (FCFs) were computed for (A) over tilde B-1(1)-->(X) over tilde (1)A(1) CF2 single vibronic level (SVL) emissions and the SVL emission spectra were simulated with the computed FCFs. When compared with the observed spectra, the simulated spectra obtained in the present investigation, which include allowance for anharmonicity and the Duschinsky effect, were found to be significantly superior to those reported previously, based on the harmonic oscillator model. Using the iterative Franck-Condon analysis procedure, with the geometry of the (X) over tilde (1)A(1) state fixed at the recently determined experimental equilibrium geometry, the geometry of the (A) over tilde B-1(1) state of CF2, which gave the best match between simulated and observed spectra, was found to be r(e)(CF)=1.317 Angstrom and theta (e)(FCF)=121.25 degrees. (C) 2001 American Institute of Physics.

Item Type: Article
Digital Object Identifier (DOI): doi:10.1063/1.1398103
Related URLs:
Keywords: least-squares algorithm, difluorocarbene cf2, spectroscopy, photoelectron, halocarbenes, frequencies, molecules, surfaces, system, band
Subjects: Q Science
Q Science > QD Chemistry
Divisions : University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 19448
Accepted Date and Publication Date:
1 October 2001Published
Date Deposited: 14 Feb 2006
Last Modified: 31 Mar 2016 11:36

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