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Title: Electrons and Hydrogen-Bond Connectivity in Liquid Water

Abstract

The network connectivity in liquid water is revised in terms of electronic signatures of hydrogen bonds (HBs) instead of geometric criteria, in view of recent x-ray absorption studies. The analysis is based on ab initio molecular-dynamics simulations at ambient conditions. Even if instantaneous threadlike structures are observed in the electronic network, they continuously reshape in oscillations reminiscent of the r and t modes in ice ({tau}{approx}170 fs). However, two water molecules initially joined by a HB remain effectively bound over many periods regardless of its electronic signature.

Authors:
 [1];  [2];  [3]
  1. Laboratoire de Physique de la Matiere Condensee et Nanostructures (LPMCN) and UMR CNRS 5586, Universite Claude Bernard Lyon 1, 69622 Villeurbanne (France)
  2. Donostia International Physics Center, Universidad del Pais Vasco, 20080 San Sebastian (Spain)
  3. (United Kingdom)
Publication Date:
OSTI Identifier:
20775023
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review Letters; Journal Volume: 96; Journal Issue: 1; Other Information: DOI: 10.1103/PhysRevLett.96.016404; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ABSORPTION SPECTRA; CHEMICAL BONDS; ELECTRONIC STRUCTURE; ELECTRONS; HYDROGEN; ICE; MOLECULAR DYNAMICS METHOD; MOLECULES; SIMULATION; WATER; X-RAY SPECTRA

Citation Formats

Fernandez-Serra, M.V., Artacho, Emilio, and Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ. Electrons and Hydrogen-Bond Connectivity in Liquid Water. United States: N. p., 2006. Web. doi:10.1103/PhysRevLett.96.016404.
Fernandez-Serra, M.V., Artacho, Emilio, & Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ. Electrons and Hydrogen-Bond Connectivity in Liquid Water. United States. doi:10.1103/PhysRevLett.96.016404.
Fernandez-Serra, M.V., Artacho, Emilio, and Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ. Fri . "Electrons and Hydrogen-Bond Connectivity in Liquid Water". United States. doi:10.1103/PhysRevLett.96.016404.
@article{osti_20775023,
title = {Electrons and Hydrogen-Bond Connectivity in Liquid Water},
author = {Fernandez-Serra, M.V. and Artacho, Emilio and Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ},
abstractNote = {The network connectivity in liquid water is revised in terms of electronic signatures of hydrogen bonds (HBs) instead of geometric criteria, in view of recent x-ray absorption studies. The analysis is based on ab initio molecular-dynamics simulations at ambient conditions. Even if instantaneous threadlike structures are observed in the electronic network, they continuously reshape in oscillations reminiscent of the r and t modes in ice ({tau}{approx}170 fs). However, two water molecules initially joined by a HB remain effectively bound over many periods regardless of its electronic signature.},
doi = {10.1103/PhysRevLett.96.016404},
journal = {Physical Review Letters},
number = 1,
volume = 96,
place = {United States},
year = {Fri Jan 13 00:00:00 EST 2006},
month = {Fri Jan 13 00:00:00 EST 2006}
}
  • The protonation scheme and the hydrogen bond connectivity in the structure of jennite were investigated by ab initio molecular dynamics simulations. The calculated statistics of hydrogen bonds at ambient conditions is consistent with the protonation scheme proposed by Bonaccorsi et al. (2004) based on the bond valence theory. The protons in the system are associated with the {identical_to}2Ca-OH linkage and H{sub 2}O molecules. The dangling Si-O bond on the bridging tetrahedra is de-protonated. The proton dynamics revealed in the molecular dynamic simulations explains the apparent discrepancies in the NMR and X-ray diffraction studies of jennite.
  • No abstract prepared.
  • No abstract prepared.
  • A molecular-level description of the unique properties of hydrogen-bond networks is critical for understanding many fundamental physico-chemical processes in aqueous environments. In this article a novel simulation approach, combining an ab-initio based force field for water with a quantum treatment of the nuclear motion, is applied to investigate hydrogen-bond dynamics in liquid water with a specific focus on the relationship of these dynamics to vibrational spectroscopy. Linear and nonlinear infrared (IR) spectra are calculated for liquid water, HOD in D2O and HOD in H2O and discussed in the context of the results obtained using other approaches that have been employedmore » in studies of water dynamics. A comparison between the calculated spectra and the available experimental data yields an overall good agreement, indicating the accuracy of the present simulation approach in describing the properties of liquid water at ambient conditions. Possible improvements on the representation of the underlying water interactions as well as the treatment of the molecular motion at the quantum-mechanical level are also discussed. This research was supported by the Division of Chemical Sciences, Biosciences and Geosciences, US Department of Energy. Battelle operates the Pacific Northwest National Laboratory for the US Department of Energy.« less
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