Photodissociation of DOBr—Time-dependent wavepacket calculations
Abstract
DOBr photoabsorption cross-sections and product rotational state distributions of the OD fragment resulting from excitation to the two lowest-lying excited singlet electronic states, 11A″ and 21A′, are computed using time-dependent wavepacket dynamics. The dynamical calculations are based on two-dimensional ab initio potential energy and transition dipole moment surfaces, in which the OD bond length is held fixed. The computed absorption band for DOBr is very similar to that of HOBr for excitation from the ground vibrational state. For vibrationally mediated photofragmentation 1A′ transition. Predictions are also made for the rotational distributions at 355 nm, where the perpendicular transition 11A″←
1A′ is dominant and no experimental product state distributions are as yet available.