Nuclear Quantum Effects in Liquid Water Are Negligible for Structure but Significant for Dynamics

Isotopic substitution, which can be realized both in experiment and computer simulations, is a direct approach to assess the role of nuclear quantum effects on the structure and dynamics of matter. Yet, the impact of nuclear quantum effects on the structure of liquid water as probed in experiment by...

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Bibliographic Details
Published inarXiv.org
Main Authors Stolte, Nore, Daru, János, bert, Harald, Behler, Jörg, Marx, Dominik
Format Paper
LanguageEnglish
Published Ithaca Cornell University Library, arXiv.org 23.10.2024
Subjects
Dynamic structural analysis
Dynamics
Heavy water
Neural networks
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Summary:Isotopic substitution, which can be realized both in experiment and computer simulations, is a direct approach to assess the role of nuclear quantum effects on the structure and dynamics of matter. Yet, 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 H\(_2\)O versus D\(_2\)O 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 unexpectedly small, on the order of 1/1000 Å, on both intramolecular and H-bonding structure 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 H\(_2\)O substantially more "liquid" than D\(_2\)O.
ISSN:2331-8422