Rotational and vibrational coupling effects on the dissociative adsorption and associative desorption dynamics of D2/Cu(111)

We investigate and discuss the effects of the coupling between molecular rotation and vibration on the dissociative adsorption and associative desorption dynamics of D-2/Cu(111), with the aid of a model Hamiltonian and the concept of a reaction path. In our model Hamiltonian, we take into account the molecular orientation dependence of the reaction path curvature in the kinetic energy term. We calculate for the dissociative adsorption probability of D-2 as a function of its initial translational energy, vibrational and rotational states, using the coupled channel method. By invoking the principle of microscopic reversibility, we obtain the corresponding associative desorption probability results for D-2 as a function of its final translational energy; vibrational and rotational states from the dissociative adsorption probability results. Furthermore, we show that the calculation results qualitatively agree with experimental results.