Analysis of the potential energy surface of Ar–NH3

Abstract

The combination of supermolecular Mo/ller–Plesset treatment with the perturbation theory of intermolecular forces is applied in the analysis of the potential energy surface of Ar–NH3. Anisotropy of the self-consistent field (SCF) potential is determined by the first-order exchange repulsion. Second-order dispersion energy, the dominating attractive contribution, is anisotropic in the reciprocal sense to the first-order exchange, i.e., minima in one nearly coincide with maxima in the other. The estimated second-order correlation correction to the exchange effect is nearly as large as a half ΔESCF in the minimum and has a ‘‘smoothing’’ effect on the anisotropy of ε(20)disp. The model which combines ΔESCF with dispersion energy (SCF+D) is not accurate enough to quantitatively describe both radial and angular dependence of interaction energy. Comparison is also made between Ar–NH3 and Ar–PH3, as well as with the Ar dimer.