Nuclear Quantum Effects in Water Reorientation and Hydrogen-Bond Dynamics

Wilkins, David M.; Manolopoulos, David E.; Pipolo, Silvio; Laage, Damien; Hynes, James T.

Type de document :

Article dans une revue scientifique

DOI :

10.1021/acs.jpclett.7b00979

URL permanente :

http://hdl.handle.net/20.500.12210/12805

Titre :

Nuclear Quantum Effects in Water Reorientation and Hydrogen-Bond Dynamics

Auteur(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]

Titre de la revue :

The Journal of Physical Chemistry Letters

Numéro :

Pagination :

2602-2607

Date de publication :

2017-05-22

Discipline(s) HAL :

Chimie/Chimie théorique et/ou physique

Résumé en anglais : [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 ...
Lire la suite >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.Lire moins >

Langue :

Anglais

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

ENSCL
CNRS
Centrale Lille
Univ. Artois
Université de Lille

Collections :

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Équipe(s) de recherche :

Modélisation et spectroscopies (MODSPEC)

Date de dépôt :

2019-09-25T14:37:48Z

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