S( ¹D ₂) atomic orbital polarization in the photodissociation of OCS at 193 nm: Construction of the complete density matrix

The absolute velocity-dependent alignment and orientation for S (D21) atoms from the photodissociation of OCS at 193 nm were measured using the dc slice imaging method. Three main peaks ascribed to specific groups of high rotational levels of CO in the vibrational ground state were found, with rotationally resolved rings in a fourth slow region ascribed to weak signals associated with excited vibrational states of CO. The observed speed-dependent Β and polarization parameters support the interpretation that there are two main dissociation processes: a simultaneous two-surface (A′ and A″) excitation and the initial single-surface (A′) excitation followed by the nonadiabatic crossing to ground state. At 193 nm photodissociation, the nonadiabatic dissociation process is strongly enhanced relative to longer wavelengths. The angle- and speed-dependent S (D21) density matrix can be constructed including the higher order (K=3,4) contributions for the circularly polarized dissociation light. This was explicitly done for selected energies and angles. It was found in one case that the density matrix is sensitively affected by the rank 4 terms, suggesting that the higher order contributions should not be overlooked for an accurate picture of the dissociation dynamics in this system.