Rotationally mediated selective adsorption in rigid rotor/rigid surface scattering

Abstract

We present a detailed investigation of a new effect in molecule/surface scattering, rotationally mediated selective adsorption, which has been first observed by Cowin et al. (J. Chem. Phys. 75 (1981) 1033) in rotationally inelastic HD/Pt (111) scattering. It is due to resonance between an asymptotically closed rotational channel and a vibrational bound state of the molecule/surface system. Exact close-coupling and diffractionally sudden calculations are performed for HD scattered from a rigid, flat and weakly corrugated surface. Both variation of the collision energy and variation of the incident angle are considered. In the latter case we include the averaging over the collision energy of the initial beam and compare qualitatively our results with the experiment. Taking into account the resonances below they j = 0 → 1 threshold we are able to explain all of the experimentally observed resonances and to assign them with the appropriate rotational-vibrational quantum numbers. The largest deviation between experimental and theoretical resonance angles is ~ 1.6° at a collision energy of E = 109 meV. An interesting interference effect is found in the case of weak surface corrugation. Although the diffractionally sudden approximation generally gives only poor results, it also reproduces this effect and provides a simple explanation of it in terms of the Breit-Wigner representation of the S-matrix.