Nuclear Quantum Effects in Liquid Water Are Marginal for Its Average Structure but Significant for Dynamics.

Abstract

Isotopic substitution, which can be realized in both experiment and computer simulations, is a direct approach to assess the role of nuclear quantum effects on the structure and dynamics of matter. However, the impact of nuclear quantum effects on the structure of liquid water as probed in experiment by comparing normal to heavy water has remained controversial. To settle this issue, we employ a highly accurate machine-learned high-dimensional neural network potential to perform converged coupled cluster-quality path integral simulations of liquid H2O versus D2O at ambient conditions. We find substantial H/D quantum effects on the rotational and translational dynamics of water, in close agreement with the experimental benchmarks. However, in stark contrast to the role for dynamics, H/D quantum effects turn out to be small, on the order of 1/1000 Å, on both average intramolecular and H-bonding structures of water. The most probable structure of water remains nearly unaffected by nuclear quantum effects, but effects on fluctuations away from average are appreciable, rendering H2O substantially more "liquid" than D2O.