Journal of Chemical Physics, Vol.107, No.1, 70-82, 1997
Spin-Orbit Branching in the Photodissociation of HBr - Time-Independent, Time-Dependent, and Semiclassical Calculations
The dynamics of the photofragmentation of HBr is treated within time-independent, time-dependent, and semiclassical methods. The calculated relative cross sections for formation of the two accessible fine-structure channels [Br(P-2(1/2)) and Br(P-2(3/2))] agree well with the experimental results, both in magnitude and in dependence on photon excitation wavelength. For relatively small photon wavelength (lambda = 193 nm), vertical excitation in the Franck-Condon region populates preferentially the A (1) Pi state, and only three states (A (1) Pi, the Omega = 1 components of the a (3) Pi and 1 (3) Sigma(+)), coupled by the spin-orbit interaction, are invoved in the dissociation process. For larger photon wavelength (lambda = 243 nm), the product branching is governed by initial excitation in both the A (1) Pi state and the a (3) Pi(Omega = 0) component. Comparison of the redistribution of the time-independent photofragment fluxes as a function of the H-Br separation with the temporal evolution of the populations within a time-dependent framework shows that the two methods, although based on a different point of view, provide equivalent mechanistic information on the dissociation process.
Keywords:LOG-DERIVATIVE METHOD;DER-WAALS COMPLEX;MOLECULAR PHOTODISSOCIATION;WAVE-PACKET;FLUX REDISTRIBUTION;SCHRODINGER-EQUATION;REACTIVE SCATTERING;PHOTO-DISSOCIATION;QUANTUM DYNAMICS;DOPPLER SPECTROSCOPY