Photodissociation dynamics of OCS near 214 nm using ion imaging

The OCS photodissociation dynamics of the dominant S((1)D2) channel near 214 nm have been studied using velocity map ion imaging. We report a CO vibrational branching ratio of 0.79:0.21 for v = 0:v = 1, indicating substantially higher vibrational excitation than that observed at slightly longer wavelengths. The CO rotational distribution is bimodal for both v = 0 and v = 1, although the bimodality is less pronounced than at longer wavelengths. Vector correlations, including rotational alignment, indicate that absorption to both the 2(1)A' (A) and 1(1)A″ (B) states is important in the lower-j part of the rotational distribution, while only 2(1)A' state absorption contributes to the upper part; this conclusion is consistent with work at longer wavelengths. Classical trajectory calculations including surface hopping reproduce the measured CO rotational distributions and their dependence on wavelength well, though they underestimate the v = 1 population. The calculations indicate that the higher-j peak in the rotational distribution arises from molecules that begin on the 2(1)A' state but make nonadiabatic transitions to the 1(1)A' (X) state during the dissociation, while the lower-j peak arises from direct photodissociation on either the 2(1)A' or the 1(1)A″ states, as found in previous work.