Importance of van der Waals interactions in liquid water.
We present ab initio molecular dynamics studies on liquid water using density functional theory in conjunction with either dispersion-corrected atom-centered potentials or empirical van der Waals corrections. Our results show that improving the description of van der Waals interactions in DFT-GGA leads to a softening of liquid water's structure with higher mobility. The results obtained with dispersion-corrected atom-centered potentials are especially encouraging. In particular, the radial distribution functions are in better agreement with experiment, and the self-diffusion coefficient increases by more than three-fold compared with the one predicted by the BLYP functional. This work demonstrates that van der Waals interactions are essential in fine-tuning both structural and dynamical properties of liquid water.
Lin
I-Chun
IC
Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne, Switzerland.
Seitsonen
Ari P
AP
Coutinho-Neto
Maurício D
MD
Tavernelli
Ivano
I
Rothlisberger
Ursula
U
D004058:Diffusion; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D007700:Kinetics; D010100:Oxygen / Q000737:chemistry; D017382:Reactive Oxygen Species / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D017382:Reactive Oxygen Species; D014867:Water; D006859:Hydrogen; D010100:Oxygen