Three-dimensional ab initio simulation of laser-induced desorption of NO from NiO(100)

Laser-induced desorption of NO molecules from a NiO(1 0 0) surface is studied on an ab initio level. Based on ab initio NiO-cluster calculations a three-dimensional potential energy surface was constructed for the electronic ground and a representative excited state. Quantum wave packet calculations on these surfaces allow the simulation of experimental velocity distributions of the desorbed NO molecules. Analysis of the wave packet dynamics demonstrates that the experimentally observed bimodality of the velocity distributions is caused by a bifurcation of the wave packet on the excited state potential, where the molecular motion parallel to the surface plays a decisive role