An accurate analytic representation of the water pair potential

Abstract

The ab initiowater dimer interaction energies obtained from coupled cluster calculations and used in the CC-pol water pair potential (Bukowski et al., Science, 2007, 315, 1249) have been refitted to a site–site form containing eight symmetry-independent sites in each monomer and denoted as CC-pol-8s. Initially, the site–site functions were assumed in a B-spline form, which allowed a precise optimization of the positions of the sites. Next, these functions were assumed in the standard exponential plus inverse powers form. The root mean square error of the CC-pol-8s fit with respect to the 2510 ab initio points is 0.10 kcal mol⁻¹, compared to 0.42 kcal mol⁻¹ of the CC-pol fit (0.010 kcal mol⁻¹ compared to 0.089 kcal mol⁻¹ for points with negative interaction energies). The energies of the stationary points in the CC-pol-8s potential are considerably more accurate than in the case of CC-pol. The water dimer vibration–rotation–tunneling spectrum predicted by the CC-pol-8s potential agrees substantially and systematically better with experiment than the already very accurate spectrum predicted by CC-pol, while specific features that could not be accurately predicted previously now agree very well with experiment. This shows that the uncertainties of the fit were the largest source of error in the previous predictions and that the present potential sets a new standard of accuracy in investigations of the water dimer.