Obtaining potential energy surfaces of an der waals molecules

Abstract

Two different methods were used to obtain a potential energy surface for the Arco molecule. One involved choosing a functional form for the repulsion and dispersion energies whose parameters were determined by a fit to experimental data. A physically justified potential that agreed with experiment could not be obtained. The other method was based on calculating ab initio interaction energies at different configurations of the molecule and interpolating between them. The resulting surface was scaled in the energy and the co-ordinates. Improved agreement was achieved for most observed bound states. Errors in the surface may have been due to an inadequate density of ab initio energies. So, how the molecular configurations chosen for interaction energy calculations affected the potential obtained was investigated. Both the co-ordinate system and the interpolation scheme also significantly affected the quality of surface obtained. The best compromise between accuracy and number of configurations, was points distributed on a regular grid in elliptic co-ordinates with Gauss-Legendre quadrature points in the angular co-ordinate. This information was employed to obtain a potential energy surface for the weakly bound HeOCS molecule which was in close agreement with experiment. A co-ordinate and energy scaling, guided by experiment, was applied to the ab initio surface. Only three scaling parameters were required due to the high quality of the initial surface.