Anchoring the water dimer potential energy surface with explicitly correlated computations and focal point analyses

Abstract

Ten stationary points on the water dimer potential energy surface have been characterized with the coupled-cluster technique which includes all single and double excitations as well as a perturbative approximation of triple excitations [CCSD(T)]. Using a triple-ζ basis set with two sets of polarization functions augmented with higher angular momentum and diffuse functions [TZ2P(f,d)+dif], the fully optimized geometries and harmonic vibrational frequencies of these ten stationary points were determined at the CCSD(T) theoretical level. In agreement with other ab initio investigations, only one of these ten stationary points is a true minimum. Of the other nine structures, three are transition structures, and the remaining are higher order saddle points. These high-level ab initio results indicate that the lowest lying transition state involved in hydrogen interchange is chiral, of C1 symmetry rather than Cs as suggested by recently developed 6D potential energy surfaces. The one- and n-particle limits of the electronic energies of these ten stationary points were probed by systematic variation of the atomic orbital basis sets and the treatment of electron correlation within the framework of the focal-point analysis of Allen and co-workers. The one-particle limit was approached via extrapolation of electronic energies computed with the augmented correlation consistent basis sets (aug-cc-pVXZ, X=D−6), and, independently, by estimating the basis set incompleteness effect with the explicitly-correlated second-order Møller-Plesset method (MP2-R12). Electron correlation was evaluated at levels as high as the Brueckner coupled cluster method with double excitations and perturbatively treated triple and quadruple excitations [BD(TQ)]. Core correlation and relativistic effects were also assessed. Consideration of the aforementioned electronic effects as well as basis set superposition error leads to an estimate of 21.0 kJ mol−1 for the electronic dissociation energy of (H2O)2.