Three-dimensional ab initio quantum dynamics of the photodesorption of CO from Cr2O3(0001): Stereodynamic effects - art. no. 077601

Having performed the first three-dimensional ab initio quantum dynamical st udy of photodesorption from solid surfaces, we gained mechanistic understan ding of the rotational alignment observed in die CO/Cr2O3(0001) system. Our study is based on potential energy surfaces obtained by embedded cluster c alculations for both the electronic ground and excited state of the adsorba te substrate complex. Stochastic wave packet calculations demonstrate the i mportance of the angular degrees of freedom for the microscopic picture of the desorption process in addition to the desorption coordinate.