skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments

Abstract

The OH stretching vibrational spectrum of water was measured in a wide range of temperatures across the triple point, 269 K < T < 296 K, using Inelastic Neutron Scattering (INS). The hydrogen projected density of states and the proton mean kinetic energy, _OH, were determined for the first time within the framework of a harmonic description of the proton dynamics. We found that in the liquid the value of _OH is nearly constant as a function of T, indicating that quantum effects on the OH stretching frequency are weakly dependent on temperature. In the case of ice, ab initio electronic structure calculations, using non-local van der Waals functionals, provided _OH values in agreement with INS experiments. We also found that the ratio of the stretching (_OH) to the total (_exp) kinetic energy, obtained from the present measurements, increases in going from ice, where hydrogen bonding is the strongest, to the liquid at ambient conditions and then to the vapour phase, where hydrogen bonding is the weakest. The same ratio was also derived from the combination of previous deep inelastic neutron scattering data, which does not rely upon the harmonic approximation, and the present measurements. We found that the ratiomore » of stretching to the total kinetic energy shows a minimum in the metastable liquid phase. This finding suggests that the strength of intermolecular interactions increases in the supercooled phase, with respect to that in ice, contrary to the accepted view that supercooled water exhibits weaker hydrogen bonding than ice.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [2];  [1]
  1. ORNL
  2. University of California, Davis
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1095761
DOE Contract Number:
AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 7
Country of Publication:
United States
Language:
English

Citation Formats

Senesi, Roberto, Flammini, Davide, Kolesnikov, Alexander I., Murray, Eamonn D., Galli, Giulia, and Andreani, Carla. The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments. United States: N. p., 2013. Web. doi:10.1063/1.4818494.
Senesi, Roberto, Flammini, Davide, Kolesnikov, Alexander I., Murray, Eamonn D., Galli, Giulia, & Andreani, Carla. The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments. United States. doi:10.1063/1.4818494.
Senesi, Roberto, Flammini, Davide, Kolesnikov, Alexander I., Murray, Eamonn D., Galli, Giulia, and Andreani, Carla. Thu . "The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments". United States. doi:10.1063/1.4818494.
@article{osti_1095761,
title = {The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments},
author = {Senesi, Roberto and Flammini, Davide and Kolesnikov, Alexander I. and Murray, Eamonn D. and Galli, Giulia and Andreani, Carla},
abstractNote = {The OH stretching vibrational spectrum of water was measured in a wide range of temperatures across the triple point, 269 K < T < 296 K, using Inelastic Neutron Scattering (INS). The hydrogen projected density of states and the proton mean kinetic energy, _OH, were determined for the first time within the framework of a harmonic description of the proton dynamics. We found that in the liquid the value of _OH is nearly constant as a function of T, indicating that quantum effects on the OH stretching frequency are weakly dependent on temperature. In the case of ice, ab initio electronic structure calculations, using non-local van der Waals functionals, provided _OH values in agreement with INS experiments. We also found that the ratio of the stretching (_OH) to the total (_exp) kinetic energy, obtained from the present measurements, increases in going from ice, where hydrogen bonding is the strongest, to the liquid at ambient conditions and then to the vapour phase, where hydrogen bonding is the weakest. The same ratio was also derived from the combination of previous deep inelastic neutron scattering data, which does not rely upon the harmonic approximation, and the present measurements. We found that the ratio of stretching to the total kinetic energy shows a minimum in the metastable liquid phase. This finding suggests that the strength of intermolecular interactions increases in the supercooled phase, with respect to that in ice, contrary to the accepted view that supercooled water exhibits weaker hydrogen bonding than ice.},
doi = {10.1063/1.4818494},
journal = {Journal of Chemical Physics},
number = 7,
volume = 139,
place = {United States},
year = {Thu Aug 01 00:00:00 EDT 2013},
month = {Thu Aug 01 00:00:00 EDT 2013}
}