Empirical assignment of absorbing electronic state contributions to OCS photodissociation product state populations from 214 to 248 nm

Abstract

The photodissociation dynamics of OCS near 214 nm for the S(1D2) channel were studied using velocity map ion imaging. Earlier studies at this wavelength were extended with new measurements of vector correlations and reanalysis of the rotational distributions in the υ = 0 and υ = 1 CO products. The results were employed to identify the contributions of the 21A′ (A) and 11A″ (B) electronic state absorptions in OCS to the population of each CO final state. The contributions of the 11A″ (B) state to the CO (υ = 1) population was found to be ∼2.5 times smaller (fB=0.14±0.04) than previous theoretical estimates, and that to the CO (υ = 0) distribution ∼1.7 times smaller (fB=0.20±0.04). A similar analysis was applied to experimental rotational distributions from the literature at photolysis wavelengths of 223 nm, 230 nm, and 248 nm.