Theory of polyatomic photodissociation in the reactive infinite order sudden approximation: Application to the Rydberg states of H3

Abstract

The photodissociation of the Rydberg states of H3 and H2D via their ground molecular electronic states are treated using the reactive infinite order sudden approximation to calculate the final scattering state. A new method for performing the sudden calculations is proposed and tested for the reactive scattering of H+H2 in the J=0 total angular momentum state. Fragment vibrational state distributions and isotopic branching ratios for the photodissociation process are presented. The line shape of the emission from the Rydberg state in the far blue wing is determined for a number of initial vibrational states of the molecule. A strong isotope effect is seen in the photodissociation of H2D.