Time-dependent quantum mechanical study of the photodissociation of HOCl and DOCl

Abstract

The results of time-dependent quantum mechanical calculations on the photodissociation of initially nonrotating HOCl and DOCl molecules are presented. Two photodissociation processes, 1 1A″←X̃ 1A′ and 2 1A′←X̃ 1A′, are considered. The dynamics are treated in a two dimensional model with a fixed O–H distance and the dissociation process is followed in a rotating body-fixed frame with total angular momentum of J′=1. The total photodissociation spectra and product rotational distributions resulting from dissociation of HOCl and DOCl originating in a number of different vibrational states are presented over a continuous range of incident photon wavelengths in the range 140–440 nm. It is found that, for HOCl, the physically more correct treatment with J′=1 leads to a qualitatively different OH product rotational distribution than that resulting from the more usual model treatment in which both initial and excited states are assumed to possess zero total angular momentum.