Quantum Dynamics of the Photodissociation of Hydrogen Halides in Rare Gas Matrices. I. The Initial State

Abstract

The present study focusses on the rotational motion of HCl molecules embedded in an Ar matrix. Assuming the HCl molecules to occupy substitutional sites in the fcc lattice, rotational wavefunctions for the vibrational and electronic ground state are obtained. Both the energetics and the spatial structures of the wavefunctions are investigated. While the J=0 and the J=1 state show relatively little matrix effects, all levels for J>1 are split by the crystal field. A possible control of the photodissociation dynamics by selection of rotational states of different spatial orientation is discussed.