Ab initio SCF and CI calculations for ground and low-lying valence and Rydberg excited states of HOCl and HClO in linear and bent nuclear conformations

Abstract

Potential curves are reported for the ground and various valence and Rydberg excited states of HOCl and HClO using abinitio SCF and CI methods. The states of HOCl are found to be generally favored over their counterparts in HClO, but the calculations indicate that small barriers nevertheless exist for angular interconversion between at least some pairs of such states; they also show that dissociation processes involving ClO bond breaking are universally favored for both HOCl and HClO. Additional calculations for the ions have also been carried out, from which the heat of formation of HOCl+ is calculated to be 237 kcal/mol and it is pointed out that a previous estimate for the corresponding HOCl quantity has subsequently been substantiated by experiment; the relative energies of the first four states of HOCl+ are found to be in good agreement with experiment as well.