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, ⟨EK⟩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 ⟨EK⟩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 ⟨EK⟩OH values in agreement with INS experiments. We also found that the ratio of the stretching (⟨EK⟩OH) to the total (⟨EK⟩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.
Skip Nav Destination
Article navigation
21 August 2013
Research Article|
August 21 2013
The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments
Roberto Senesi;
Roberto Senesi
a)
1Dipartimento di Fisica e Centro NAST,
Università degli Studi di Roma “Tor Vergata
,” Via della Ricerca Scientifica 1, 00133 Roma, Italy
2
Consiglio Nazionale delle Ricerche
, CNR-IPCF, Sezione di Messina, Italy
Search for other works by this author on:
Davide Flammini;
Davide Flammini
1Dipartimento di Fisica e Centro NAST,
Università degli Studi di Roma “Tor Vergata
,” Via della Ricerca Scientifica 1, 00133 Roma, Italy
Search for other works by this author on:
Alexander I. Kolesnikov;
Alexander I. Kolesnikov
3
Neutron Scattering Science Division
, Oak Ridge National Laboratory, Tennessee 37831-6460, USA
Search for other works by this author on:
Éamonn D. Murray;
Éamonn D. Murray
4
University of California
, Davis, California 95616, USA
Search for other works by this author on:
Giulia Galli;
Giulia Galli
4
University of California
, Davis, California 95616, USA
Search for other works by this author on:
Carla Andreani
Carla Andreani
1Dipartimento di Fisica e Centro NAST,
Università degli Studi di Roma “Tor Vergata
,” Via della Ricerca Scientifica 1, 00133 Roma, Italy
Search for other works by this author on:
a)
Electronic mail: roberto.senesi@uniroma2.it
J. Chem. Phys. 139, 074504 (2013)
Article history
Received:
May 17 2013
Accepted:
August 01 2013
Citation
Roberto Senesi, Davide Flammini, Alexander I. Kolesnikov, Éamonn D. Murray, Giulia Galli, Carla Andreani; The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments. J. Chem. Phys. 21 August 2013; 139 (7): 074504. https://doi.org/10.1063/1.4818494
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
A theory of pitch for the hydrodynamic properties of molecules, helices, and achiral swimmers at low Reynolds number
Anderson D. S. Duraes, J. Daniel Gezelter
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Electronic structure simulations in the cloud computing environment
Eric J. Bylaska, Ajay Panyala, et al.
Related Content
Spherical momentum distribution of the protons in hexagonal ice from modeling of inelastic neutron scattering data
J. Chem. Phys. (January 2012)
Phonon-assisted proton tunneling in the hydrogen-bonded dimeric selenates of Cs3H(SeO4)2
J. Chem. Phys. (April 2020)
Proton dynamics in ice VII at high pressures
J. Chem. Phys. (July 2013)
Σ − photoproduction on the neutron: Results from CLAS
AIP Conference Proceedings (April 2002)
Electroproduction of π0 at high momentum transfers in non-resonant region with CLAS
AIP Conference Proceedings (October 2013)