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A surprisingly simple correlation between the classical and quantum structural networks in liquid water


Hamm, Peter; Fanourgakis, George S; Xantheas, Sotiris S (2017). A surprisingly simple correlation between the classical and quantum structural networks in liquid water. Journal of Chemical Physics, 147(6):064506.

Abstract

Nuclear quantum effects in liquid water have profound implications for several of its macroscopic properties related to the structure, dynamics, spectroscopy, and transport. Although several of water's macroscopic properties can be reproduced by classical descriptions of the nuclei using interaction potentials effectively parameterized for a narrow range of its phase diagram, a proper account of the nuclear quantum effects is required to ensure that the underlying molecular interactions are transferable across a wide temperature range covering different regions of that diagram. When performing an analysis of the hydrogen-bonded structural networks in liquid water resulting from the classical (class) and quantum (qm) descriptions of the nuclei with two interaction potentials that are at the two opposite ends of the range in describing quantum effects, namely the flexible, pair-wise additive q-TIP4P/F, and the flexible, polarizable TTM3-F, we found that the (class) and (qm) results can be superimposed over the temperature range T = 250-350 K using a surprisingly simple, linear scaling of the two temperatures according to T-(qm) = alpha T-(class) + Delta T, where alpha = 0.99 and Delta T = -6 K for q-TIP4P/F and alpha = 1.24 and Delta T = -64 K for TTM3-F. This simple relationship suggests that the structural networks resulting from the quantum and classical treatment of the nuclei with those two very different interaction potentials are essentially similar to each other over this extended temperature range once a model-dependent linear temperature scaling lawis applied.

Abstract

Nuclear quantum effects in liquid water have profound implications for several of its macroscopic properties related to the structure, dynamics, spectroscopy, and transport. Although several of water's macroscopic properties can be reproduced by classical descriptions of the nuclei using interaction potentials effectively parameterized for a narrow range of its phase diagram, a proper account of the nuclear quantum effects is required to ensure that the underlying molecular interactions are transferable across a wide temperature range covering different regions of that diagram. When performing an analysis of the hydrogen-bonded structural networks in liquid water resulting from the classical (class) and quantum (qm) descriptions of the nuclei with two interaction potentials that are at the two opposite ends of the range in describing quantum effects, namely the flexible, pair-wise additive q-TIP4P/F, and the flexible, polarizable TTM3-F, we found that the (class) and (qm) results can be superimposed over the temperature range T = 250-350 K using a surprisingly simple, linear scaling of the two temperatures according to T-(qm) = alpha T-(class) + Delta T, where alpha = 0.99 and Delta T = -6 K for q-TIP4P/F and alpha = 1.24 and Delta T = -64 K for TTM3-F. This simple relationship suggests that the structural networks resulting from the quantum and classical treatment of the nuclei with those two very different interaction potentials are essentially similar to each other over this extended temperature range once a model-dependent linear temperature scaling lawis applied.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:14 August 2017
Deposited On:09 Mar 2018 12:56
Last Modified:18 Apr 2018 11:49
Publisher:American Institute of Physics
ISSN:0021-9606
Funders:U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, Swiss National Science Foundation (SNF) through the NCCR MUST, Office of Science of the U.S. Department of Energy
OA Status:Closed
Publisher DOI:https://doi.org/10.1063/1.4993166
Project Information:
  • : Funder
  • : Grant ID
  • : Project TitleU.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation (SNF) through the NCCR MUST
  • : Funder
  • : Grant ID
  • : Project TitleOffice of Science of the U.S. Department of Energy

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