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Title: Quantum fluctuations and isotope effects in ab initio descriptions of water

Abstract

Isotope substitution is extensively used to investigate the microscopic behavior of hydrogen bonded systems such as liquid water. The changes in structure and stability of these systems upon isotope substitution arise entirely from the quantum mechanical nature of the nuclei. Here, we provide a fully ab initio determination of the isotope exchange free energy and fractionation ratio of hydrogen and deuterium in water treating exactly nuclear quantum effects and explicitly modeling the quantum nature of the electrons. This allows us to assess how quantum effects in water manifest as isotope effects, and unravel how the interplay between electronic exchange and correlation and nuclear quantum fluctuations determine the structure of the hydrogen bond in water.

Authors:
;  [1];  [2]
  1. Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305 (United States)
  2. Laboratory of Computational Science and Modeling, École Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland)
Publication Date:
OSTI Identifier:
22308381
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DEUTERIUM; ELECTRONS; FLUCTUATIONS; FREE ENERGY; HYDROGEN; LIQUIDS; SIMULATION; STABILITY; WATER

Citation Formats

Wang, Lu, Markland, Thomas E., E-mail: tmarkland@stanford.edu, and Ceriotti, Michele, E-mail: michele.ceriotti@epfl.ch. Quantum fluctuations and isotope effects in ab initio descriptions of water. United States: N. p., 2014. Web. doi:10.1063/1.4894287.
Wang, Lu, Markland, Thomas E., E-mail: tmarkland@stanford.edu, & Ceriotti, Michele, E-mail: michele.ceriotti@epfl.ch. Quantum fluctuations and isotope effects in ab initio descriptions of water. United States. doi:10.1063/1.4894287.
Wang, Lu, Markland, Thomas E., E-mail: tmarkland@stanford.edu, and Ceriotti, Michele, E-mail: michele.ceriotti@epfl.ch. Sun . "Quantum fluctuations and isotope effects in ab initio descriptions of water". United States. doi:10.1063/1.4894287.
@article{osti_22308381,
title = {Quantum fluctuations and isotope effects in ab initio descriptions of water},
author = {Wang, Lu and Markland, Thomas E., E-mail: tmarkland@stanford.edu and Ceriotti, Michele, E-mail: michele.ceriotti@epfl.ch},
abstractNote = {Isotope substitution is extensively used to investigate the microscopic behavior of hydrogen bonded systems such as liquid water. The changes in structure and stability of these systems upon isotope substitution arise entirely from the quantum mechanical nature of the nuclei. Here, we provide a fully ab initio determination of the isotope exchange free energy and fractionation ratio of hydrogen and deuterium in water treating exactly nuclear quantum effects and explicitly modeling the quantum nature of the electrons. This allows us to assess how quantum effects in water manifest as isotope effects, and unravel how the interplay between electronic exchange and correlation and nuclear quantum fluctuations determine the structure of the hydrogen bond in water.},
doi = {10.1063/1.4894287},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}