Decay of CS2 and OCS after sulphur is photoexcitation .2. Dissociation channels and kinematics

CS2 and OCS molecules were excited and fragmented by x-rays of variable energy around the sulphur Is threshold (2478 eV). Coincident detection of three ionic fragments by a time-of-flight mass spectrometer enabled the determination of branching ratios for 18 dissociation channels with total ionic charges between 2 and 7. While the electronic de-excitation is similar in both molecules (see the preceding paper), the dissociation shows differences, notably a more asymmetric distribution of charge onto the fragments of OCS. Branching among channels of the same total charge is independent of photon energy although the dominant de-excitation cascades are not. This is interpreted as an indication of strong interchannel mixing. A simple, parameter-free Coulomb explosion model to simulate the dissociative kinematics is described. Detailed results based on this model give, contrary to opinions to be found in the literature, very good agreement with observed momentum correlations whereas maximum kinetic energies are somewhat overestimated for channels of higher total charge.