Dynamics of Hl photodissociation in the A band absorption via H-atom Doppler spectroscopy

The dynamics of HI photodissociation following absorption in the A band (200 to 300 nm) was investigated by Doppler spectroscopy at the Lyman cu transition of the H-atom photofragments. Measurements of both the branching ratios for the formation of spin-orbit excited I(P-2(1/2)) and ground state I(P-2(3/2)) atoms and the angular distributions of the recoil velocity for these two photofragment channels were obtained at nine photolysis wavelengths between 212.5 and 266 nm. These results show that ground state products result from a transition of perpendicular symmetry (Delta Omega=1), while the excited state atoms are produced from a parallel transition (Delta Omega=0). These experimental results, in combination with total absorption cross section data obtained prior to the present study, have enabled a calculation of the potential curves for the dissociative excited stales. The outcome of the calculation was found to be in good qualitative agreement with the model of HI electronic structure originally suggested by Mulliken. (C) 1998 American Institute of Physics. [S0021-9606(98)01441-X].