An algebraic variational approach to dissociative adsorption of a diatomic molecule on a smooth metal surface

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Abstract
A general theoreticaltreatment employing a time‐independent algebraic variational method (S‐matrix Kohn variational method) for dissociativeadsorption of a diatomic molecule on a smooth metal surface is presented. The time‐independent scatteringtreatment using the S‐matrix Kohn variational method naturally enables one to obtain accurate state‐to‐state reaction probabilities for dissociativeadsorption of molecules on surfaces. In this paper, the S‐matrix Kohn variational method is adapted to the 3D dissociativeadsorption of H2 on Ni(100) surfacetreated as a flat surface, and the state‐to‐state transition probabilities are obtained. The dependence of the dissociation probabilities on the initial rovibrational state of H2(vjm) is examined. As a result of flat surface approximation, which conserves the rotation quantum number j z =m, the exchange symmetry of H2 has an important consequence on the vibrations of the adsorbates. Specially if the rotational state of H2 satisfies the condition j+m=odd, the vibrational quantum number of two adsorbed hydrogen atoms must be different. The orientational effect of rotation is such that the in‐plane rotation (m=j) is more favorable for molecular dissociation on surface than the out‐of‐plane rotation (m=0).