Photodissociation and predissociation processes in OH: a time-dependent quantum mechanical study

Abstract

Photodissociation from the ground vibrational and ground electronic state (X²Π) and spin-orbit induced predissociation from the A ²∑⁺ state of OH have been studied using the time-dependent quantum mechanical approach. Photodissociation cross sections computed thus are in accord with the time-independent quantal results and are comparable to the experimental results. Predissociation linewidths (Γ) computed using the wavepacket golden rule treatment corresponding to v'=1-7 of A²∑⁺ state are also in agreement with most of the earlier theoretical results. For v'=1-3, there is a general agreement between experiment and theory but for v'=4, the difference is substantial. For v'=5-7, there are no experimental results available. The results obtained from our calculations indicate that the inclusion of R-dependence of the spin-orbit coupling plays an important role in deciding the v' dependence of Γ.