Photodissociation of water on rutile (110): A wave packet approach based on first principles

Abstract

The photodissociation of water on rutile (110) is studied from first principles. Using an embedded cluster approach, the motion of one hydrogen atom with a fixed OH group served as a model system. The ground and an electronically excited state are calculated on a CASSCF level of theory, explicitly accounting for the multi-reference character of the wave function during bond breaking. The dynamics is simulated by solving the time-dependent Schrödinger equation for a wave packet moving on the electronic potential energy surface. Photodissociation probabilities of water are calculated for hydrogen, deuterium and tritium, thereby revealing significant isotope effects.