Quantum effects in liquid water from an ab initio-based polarizable force field

Abstract

The importance of quantum effects as well as the accuracy of the ab initio-based polarizable TTM2.1-F force field in describing liquid water are quantitatively assessed by a detailed analysis of the temperature dependence of several thermodynamic and dynamical properties computed using the path-integral molecular dynamics and centroid molecular dynamics methods. The results show that quantum effects are not negligible even at relatively high temperatures, and their inclusion in simulations with the TTM2.1-F water model is necessary to achieve a more accurate description of the liquid properties. Comparison with the results reported in the literature for empirical, nonpolarizable force fields demonstrates that the effects of the nuclear quantization on the dielectric constant are dependent in part on how the electronic polarization is described in the underlying water model, while comparison with other ab initio-based force fields shows that the TTM2.1-F model provides an overall accurate description of liquid water. Analysis of the isotope effect on the dynamical properties does not display significant temperature dependence. This suggests that the contribution of quantum tunneling, which has been proposed as a possible cause for the different orientational dynamics observed for the HDO:H2O and HDO:D2O systems, appears to be small.