Title :

Revisiting a many-body model for water based on a single polarizable site: From gas phase clusters to liquid and air/liquid water systems

Author(s) :

Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Flament, Jean-Pierre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Masella, Michel [Auteur]
Institut de Biologie et de Technologies de Saclay [IBITECS]

Journal title :

The Journal of Chemical Physics

Pages :

114502

Publisher :

American Institute of Physics

Publication date :

2013-09-18

ISSN :

0021-9606

HAL domain(s) :

Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

We present a revised version of the water many-body model TCPE [M. Masella and J.-P. Flament, J. Chem. Phys.107, 9105 (Year: 1997)], which is based on a static three charge sites and a single polarizable site to model the ...
Show more >We present a revised version of the water many-body model TCPE [M. Masella and J.-P. Flament, J. Chem. Phys.107, 9105 (Year: 1997)], which is based on a static three charge sites and a single polarizable site to model the molecular electrostatic properties of water, and on an anisotropic short range many-body energy term specially designed to accurately model hydrogen bonding in water. The parameters of the revised model, denoted TCPE/2013, are here developed to reproduce the ab initio energetic and geometrical properties of small water clusters (up to hexamers) and the repulsive water interactions occurring in cation first hydration shells. The model parameters have also been refined to reproduce two liquid water properties at ambient conditions, the density and the vaporization enthalpy. Thanks to its computational efficiency, the new model range of applicability was validated by performing simulations of liquid water over a wide range of temperatures and pressures, as well as by investigating water liquid/vapor interfaces over a large range of temperatures. It is shown to reproduce several important water properties at an accurate enough level of precision, such as the existence liquid water density maxima up to a pressure of 1000 atm, the water boiling temperature, the properties of the water critical point (temperature, pressure, and density), and the existence of a "singularity" temperature at about 225 K in the supercooled regime. This model appears thus to be particularly well-suited for characterizing ion hydration properties under different temperature and pressure conditions, as well as in different phases and interfaces.Show less >

Language :

Anglais

Popular science :

Non

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL