Analysis of laser-induced fluorescence spectra of the (B)over-tilde((2)A '')-(X)over-tilde((2)A '') transition with calculated Franck-Condon factors of CH2CFO

Geometry optimization and vibrational analysis of the ground and lowest thr ee excited states of the fluorovinoxy radical (CH2CFO) were performed by th e CASSCF method. Franck-Condon factors of the (B) over tilde-(X) over tilde transition were calculated and then subjected to the assignment of vibroni c bands in laser-induced fluorescence spectra. The calculated Franck-Condon factors satisfactorily reproduced the measured fluorescence excitation and dispersed fluorescence spectra after a small correction of the relative di splacement between normal coordinate systems of two states. The effect of C -C torsion on predissociation in the (B) over tilde state was studied with calculated potential energy curves along the coordinate. (C) 1998 Elsevier Science B.V. All rights reserved.