Photodissociation dynamics of H2S(D2S) following excitation within its first absorption continuum

Abstract

The technique of H(D) atom photofragment translational spectroscopy has been applied to the photodissociation of H2S(D2S) following excitation at a number of wavelengths in its first absorption continuum. The respective bond dissociation energies were determined as D0(H–SH)=3.90±0.03 eV and D0(D–SD)=4.00±0.02 eV. The measured vibrational energy disposal in the partner ground state SH(SD) fragments and the product angular distributions support and extend the earlier results of van Veen et al. [Chem. Phys. 74, 261 (1983)], while the deduced rotational and spin–orbit state population distributions in these fragments appear to be generally consistent with the recent measurements of Weiner et al. [J. Chem. Phys. 90, 1403 (1989)]. We present a schematic adiabatic potential energy surface for the dissociative 1A″ excited state via which it is possible to rationalize virtually all existing dynamical measurements relating to this fragmentation process.