Hydrogen bonding definitions and dynamics in liquid water

Rajiv Kumar, J. R. Schmidt, J. L. Skinner

Research output: Contribution to journalArticle

369 Citations (Scopus)

Abstract

X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point chargeextended (SPCE) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPCE water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.

Original languageEnglish (US)
Article number204107
JournalJournal of Chemical Physics
Volume126
Issue number20
DOIs
StatePublished - 2007

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Hydrogen bonds
Water
Liquids
hydrogen
liquids
water
hydrogen bonds
Bond number
Vibrational spectroscopy
Structural relaxation
Neutron diffraction
x ray scattering
Dimers
Electronic structure
neutron diffraction
Raman scattering
cut-off
dimers
Raman spectra
electronic structure

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Hydrogen bonding definitions and dynamics in liquid water. / Kumar, Rajiv; Schmidt, J. R.; Skinner, J. L.

In: Journal of Chemical Physics, Vol. 126, No. 20, 204107, 2007.

Research output: Contribution to journalArticle

Kumar, Rajiv ; Schmidt, J. R. ; Skinner, J. L. / Hydrogen bonding definitions and dynamics in liquid water. In: Journal of Chemical Physics. 2007 ; Vol. 126, No. 20.
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