EXACT QUANTUM AND TIME-DEPENDENT HARTREE STUDIES OF THE HBR/LIF(001) PHOTODISSOCIATION DYNAMICS

Photodissociation dynamics of HBr adsorbed on a LiF(001) surface are investigated using both exact and time-dependent Hartree (TDH) methods on realistic potential energy surfaces. The dissociation dynamics are restricted in two dimensions and two coupled dissociative states of the adsorbate are included. The wave packets are propagated on numerical grids, and fast Fourier transform (FFT) and discrete variable representation (DVR) are used to calculate the action of the Hamiltonian. In the TDH treatment, each excited electronic state is represented by a single nuclear configuration. Final radial, angular, and momentum distributions of the H fragment are calculated. Comparisons between the exact and TDH results reveal that the agreement between the two is generally reasonable and is better for highly averaged quantities. Results also show that nonadiabatic transition dynamics are correctly reproduced by the TDH approximation. Finally, the calculated results are found consistent with the experimental observations.