Coping with the anisotropy in the analytical representation of an ab initio potential energy surface for the Cl2 dimer

Abstract

The intermolecular potential energy surface (PES) of the Cl₂ dimer is calculated at the MP2/aTZ + b level of ab initio theory. A quantitative measure is proposed for comparison of the anisotropy of PESs of different systems at different intermolecular distances. A high degree of anisotropy at short and intermediate distances results in the failure of fitting strategies that are based on the angular expansion of the potential energy. To tackle this problem, a step-by-step fitting strategy is designed for analytical representation of the PES. The global minimum energy configuration of the dimer is found to be a distorted L-shape structure with a well depth of around 615 cm⁻¹. The PES is finally scaled to minimize deviations between calculated and experimental second virial coefficients.