Three-DimensionalAb InitioQuantum Dynamics of the Photodesorption of CO fromCr2O3(0001): Stereodynamic Effects

Having performed the first three-dimensional ab initio quantum dynamical study of photodesorption from solid surfaces, we gained mechanistic understanding of the rotational alignment observed in the $\mathrm{CO}/{\mathrm{Cr}}_2{\mathrm{O}}_3\left(0001\right)$ system. Our study is based on potential energy surfaces obtained by embedded cluster calculations for both the electronic ground and excited state of the adsorbate substrate complex. Stochastic wave packet calculations demonstrate the importance of the angular degrees of freedom for the microscopic picture of the desorption process in addition to the desorption coordinate.