PNNL

Abstract

In a previous paper [L. Sun, P. de Sainte Claire, O. Meroueh, and W. L Hase, J. Chem. Phys. 114, 535 (2001], a classical trajectory simulation was reported of CH4 desorption from Ni{111} by Ar-atom collisions. At an incident angle ?iof 60° (with respect to the surface normal), the calculated collision-induced desorption (CID) cross sections are in excellent agreement with experiment. However, for smaller incident angles the calculated cross sections are larger than the experimental values and for normal collisions, ?i=0°, the calculated cross sections are approximately a factor of 2 larger. This trajectory study used an analytic function for the Ar +Ni(s) intermolecular potential which gives an Ar–Ni{111} potential energy minimum which is an order of magnitude too deep. In the work reported here, the previous trajectory study is repeated with an Ar+Ni(s) analytic intermolecular potential which gives an accurate Ar–Ni{111} potential energy minimum and also has a different surface corrugation than the previous potential. Though there are significant differences between the two Ar+Ni(s) analytic potentials, they have no important effects on the CID dynamics and the cross sections reported here are nearly identical to the previous values. Zero-point energy motions of the surface and the CH4 – Ni(s) intermolecular modes are considered in the simulation and they are found to have a negligible effect on the CID cross sections. Calculations of the intermolecular potential between CH4 and a Ni atom, at various levels of theory, suggest that there are substantial approximations in the ab initio calculation used to develop the CH4 1Ni{111} potential. The implication is that the differences between the trajectory and experimental CID cross sections may arise from an inaccurate CH4 {Ni} potential used in the trajectory simulation.