An experimental and ab initio study of the electronic spectrum of the jet-cooled F2BO free radical.

Abstract

We have studied the B̃ (2)A1-X̃ (2)B2 laser-induced fluorescence (LIF) spectrum of the jet-cooled F2BO radical for the first time. The transition consists of a strong 0(0)(0)band at 446.5 nm and eight weak sequence bands to shorter wavelengths. Single vibronic level emission spectra obtained by laser excitation of individual levels of the B̃ state exhibit two electronic transitions: a very weak, sparse B̃-X̃ band system in the 450-500 nm region and a stronger, more extensive set of B̃ (2)A1-à (2)B1 bands in the 580-650 nm region. We have also performed a series of high level ab initio calculations to predict the electronic energies, molecular structures, vibrational frequencies, and rotational and spin-rotation constants in the X̃ (2)B2, à (2)B1 and B̃ (2)A1 electronic states as an aid to the analysis of the experimental data. The theoretical results have been used as input for simulations of the rotationally resolved B̃ (2)A1-X̃ (2)B2 0(0)(0) LIF band and Franck-Condon profiles of the LIF and single vibronic level emission spectra. The agreement between the simulations obtained with purely ab initio parameters and the experimental spectra validates the geometries calculated for the ground and excited states and the conclusion that the radical has C2v symmetry in the X̃, Ã, and B̃ states. The spectra provide considerable new information about the vibrational energy levels of the X̃ and à states, but very little for the B̃ state, due to the very restrictive Franck-Condon factors in the LIF spectra.