The Combined Influence of Nuclear Quantum Effects and van der Waals\n Interactions on the Structure of Ambient Water

2014/02/11 by Jeffrey M. McMahon, McMahon, Jeffrey M., Miguel A. Morales +5
Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Quantum Electrodynamics and Casimir Effect #Quantum, superfluid, helium dynamics #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.1402.2697

openalex publication_date 2014/02/11 · openalex created_date 2022/08/31 · openalex updated_date 2026/07/28

Abstract

Path-integral molecular dynamics simulations based on density functional\ntheory employing exchange-correlation density functionals capable of treating\nnonlocal van der Waals (vdW) interactions self-consistently provide a\nremarkably accurate description of ambient water. Moreover, they suggest that\nwater's structure may be impacted by a combined influence between nuclear\nquantum effects and vdW interactions. The latter strongly favor the formation\nof a high-density liquid, whereas the inclusion of the former mitigates this by\ndecreasing the mean hydrogen-bond (H-bond) distance. Examining the structure of\nwater reveals that while the major fraction of molecules do in fact exhibit the\ntraditional picture of near-tetrahedral coordination, the liquid considerably\nsofter than previously simulations have suggested, including a much lower\nproportion of molecules double-donating H-bonds as well as a much larger\ndistribution of their angles.\n

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