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Analysis Of The Potential Energy Surface Of Ar–Nh3, G. Chalasinski, S. M. Cybulski, M. M. Szczesniak, Steve Scheiner

Steve Scheiner

The combination of supermolecular Møller–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 ΔE^SCF in the minimum and has a ‘‘smoothing’’ effect on the anisotropy of …