Ab initio intermolecular potential energy surfaces of the water-rare gas atom complexes

Highly accurate analytical intermolecular potential energy surfaces (PESs) of the complexes composed of the water molecule and the rare gas (Rg) atom are presented for Rg = He , Ne, Ar, and Kr. These PESs were scanned using the supermolecule coupled cluster singles and doubles including connected triples method [CCSD(T)]. Efficient basis sets including the bond functions ( 3 s 3 p 2 d 1 f 1 g ) enabled the calculation of more than 430 single-point interaction energies for each complex. These energies were utilized to construct the analytical many-body representations of the PESs. They were refined using the interaction energies evaluated at the complete basis set limit in the PES stationary points. In addition, the corrections from the core correlation were calculated for the complexes including He, Ne, and Ar. The many-body PES of XeH 2 O was built using the ab initio energy values reported by Wen and Jäger [ J. Phys. Chem. A 110 , 7560 ( 2006 ) ]. The clear regularities of the equilibrium structure and the potential barriers were found in the RgH 2 O series. A comparison of the ab initio and experimental PESs of ArH 2 O [ R. C. Cohen and R. J. Saykally , J. Chem. Phys. 98 , 6007 ( 1993 ) ] reveals their close similarity, except for the potential barriers corresponding to the planar saddle points. Their energetic order is different in both PESs. This suggests that an alternative PES with the reversed barriers, consistent with the ab initio ones, could be derived from the experimental data.