On the usefulness of generalised quantum chemical valence parameters in monitoring the course of a chemical reaction: a case study of the photochemical decomposition of HNO in excited states

Abstract

A variant of the orthogonal gradient method of orbital optimization in the INDO-MCSCF framework has been used to study the photochemical decomposition of the HNO molecule into H + NO in the lowest1.3A? states. A complete geometry optimization has been carried out at all points of the reaction path which appears to be almost barrierless. The one-electron density matrix extracted from the optimized wavefunction at each point has been used to generate the relevant sets of quantum chemical valence parameters. A sharp transition is noted in the N-H bond order and hydrogen free valence index when plotted as functions of rNH. This enables us to locate the transition region easily.