Time-independent quantum dynamics for diatom–surface scattering

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Abstract
Two time‐independent quantum reactive scattering methods, namely, the S‐matrix Kohn technique to compute the full S‐matrix, and the absorbing boundary Green’s function method to compute cumulative reaction probabilities, are applied here to the case of diatom–surface scattering. In both cases a discrete variable representation for the operators is used. We test the methods for two‐ and three‐dimensional uncorrugated potential energy surfaces, which have been used earlier by Halstead et al. [J. Chem. Phys. 93, 2359 (1990)] and by Sheng et al. [J. Chem. Phys. 97, 684 (1992)] in studies of H2 dissociating on metal substrates with theoretical techniques different from those applied here. We find overall but not always perfect agreement with these earlier studies. Based on ab initio data and experiment, a new, six‐dimensional potential energy surface for the dissociative chemisorption of H2 on Ni(100) is proposed. Two‐ and three‐dimensional cuts through the new potential are performed to illustrate special dynamical aspects of this particular molecule–surface reaction: (i) the role of corrugation effects, (ii) the importance of the ‘‘cartwheel’’ rotation of H2 , and (iii) the role of the ‘‘helicopter’’ degree of freedom for the adsorbing molecule.