Nuclear Quantum Effects in Water Reorientation ...
Document type :
Article dans une revue scientifique
Permalink :
Title :
Nuclear Quantum Effects in Water Reorientation and Hydrogen-Bond Dynamics
Author(s) :
Wilkins, David M. [Auteur]
Manolopoulos, David E. [Auteur]
Pipolo, Silvio [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Laage, Damien [Auteur]
Hynes, James T. [Auteur]
Manolopoulos, David E. [Auteur]
Pipolo, Silvio [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Laage, Damien [Auteur]
Hynes, James T. [Auteur]
Journal title :
The Journal of Physical Chemistry Letters
Volume number :
8
Pages :
2602-2607
Publication date :
2017-05-22
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
English abstract : [en]
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 ...
Show more >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 ∼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 OO 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.Show less >
Show more >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 ∼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 OO 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.Show less >
Language :
Anglais
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
ENSCL
CNRS
Centrale Lille
Univ. Artois
Université de Lille
CNRS
Centrale Lille
Univ. Artois
Université de Lille
Collections :
Research team(s) :
Modélisation et spectroscopies (MODSPEC)
Submission date :
2019-09-25T14:37:48Z