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

CASSCF/MRCI/aug-cc-pVQZ(no g) and RCCSD(T)/aug-cc-pVQZ potential energy fun ctions 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 var iational calculations, employing Watson's Hamiltonian for a nonlinear molec ule and anharmonic vibrational wave functions expressed as linear combinati ons 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 lev el (SVL) emissions and the SVL emission spectra were simulated with the com puted FCFs. When compared with the observed spectra, the simulated spectra obtained in the present investigation, which include allowance for anharmon icity and the Duschinsky effect, were found to be significantly superior to those reported previously, based on the harmonic oscillator model. Using t he iterative Franck-Condon analysis procedure, with the geometry of the (X) over tilde (1)A(1) state fixed at the recently determined experimental equ ilibrium 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.