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research article

Nuclear Quantum Effects in Water Reorientation and Hydrogen-Bond Dynamics

Wilkins, David M.  
•
Manolopoulos, David E.
•
Pipolo, Silvio
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2017
The Journal of Physical Chemistry Letters

We combine classical and ring polymer molecular dynamics simulations with the molecular jump model to provide a molecular description of the nuclear quantum effects (NQEs) on water reorientation and hydrogen-bond dynamics in liquid H2O and D2O. We show that while the net NQE is negligible in D2O, it leads to a similar to 13% acceleration in H2O dynamics compared to a classical description. Large angular jumps exchanging hydrogen-bond partners are the dominant reorientation pathway (just as in a classical description); the faster reorientation dynamics arise from the increased jump rate constant. NQEs do not change the jump amplitude distribution, and no significant tunneling is found. The faster jump dynamics are quantitatively related to decreased structuring of the 00 radial distribution function when NQEs are included. This is explained, via a jump model analysis, by competition between the effects of water's librational and OH stretch mode zero-point energies on the hydrogen-bond strength.

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Type
research article
DOI
10.1021/acs.jpclett.7b00979
Web of Science ID

WOS:000403741800010

Author(s)
Wilkins, David M.  
•
Manolopoulos, David E.
•
Pipolo, Silvio
•
Laage, Damien
•
Hynes, James T.
Date Issued

2017

Publisher

Amer Chemical Soc

Published in
The Journal of Physical Chemistry Letters
Volume

8

Issue

12

Start page

2602

End page

2607

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
July 10, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/138973
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