Laser-induced fluorescence of the trans-CHBrCHO radical.

Abstract

A new laser-induced fluorescence spectrum was observed in the region of 350 nm-360 nm. The spectrum was observed in the reaction between the CHBrCHBr and OH radicals and in the reaction of CHBrCHBr and CH2CHBr with atomic oxygen O(3P). The spectrum was assigned to the B̃--X̃ transition of the trans-CHBrCHO (trans-2-bromovinoxy) radical. The B̃--X̃ electronic transition energy (T0) was 28 542 cm-1, which was 242 cm-1 lower than that of the unsubstituted vinoxy radical (CH2CHO). From an analysis of the laser-induced single vibronic level fluorescence aided by ab initio calculations, some of the vibrational frequencies were assigned to the ground electronic state ν3 (C-O str.) = 1581 cm-1, ν6 (C-C str.) = 1130 cm-1, and ν8 (C-C-O bend.) = 409 cm-1. The fluorescence lifetimes of the excited B̃ state were 35 ns-75 ns, depending on the excited vibrational modes, implying that predissociation had accelerated as the energy level (v') increased.