Laser detection of spin-polarized hydrogen from HCl and HBr photodissociation: comparison of H- and halogen-atom polarizations.

Thermal HCl and HBr molecules were photodissociated using circularly polarized 193 nm light, and the speed-dependent spin polarization of the H-atom photofragments was measured using polarized fluorescence at 121.6 nm. Both polarization components, described by the a(0)(1)(perpendicular) and Re[a(1)(1)(parallel, perpendicular)] parameters which arise from incoherent and coherent dissociation mechanisms, are measured. The values of the a(0)(1)(perpendicular) parameter, for both HCl and HBr photodissociation, are within experimental error of the predictions of both ab initio calculations and of previous measurements of the polarization of the halide cofragments. The experimental and ab initio theoretical values of the Re[a(1)(1)(parallel, perpendicular)] parameter show some disagreement, suggesting that further theoretical investigations are required. Overall, good agreement occurs despite the fact that the current experiments photodissociate molecules at 295 K, whereas previous measurements were conducted at rotational temperatures of about 15 K.