Dynamics of charge transfer states on metal surfaces: the competition between reactivity and quenching.

Abstract

The dynamics of excited states of adsorbates on surfaces caused by charge transfer is studied. Both negative and positive charge transfer processes are possible. In particular we are interested in positive charge transfer from a metal surface to molecular or atomic oxygen adsorbed on the surface. Once the negatively charged oxygen on the surface loses an electron it becomes chemically activated. The ability of this species to react depends on the quenching time or back transfer. The analysis of these processes is based on a set of diabatic potential energy surfaces each representing a different charged oxygen species. The dynamics is followed by solving the multichannel time-dependent Schrödinger equation or Liouville von Neumann equation. Due to the nonadiabatic character of these reactions large isotope effects are predicted.