How Van Der Waals Interactions Determine the Unique Properties of Water

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2016 Jul 13

PMID 27402761

Citations 56

Authors

Tobias Morawietz

Andreas Singraber

Christoph Dellago

Jorg Behler

Affiliations

Soon will be listed here.

Abstract

Whereas the interactions between water molecules are dominated by strongly directional hydrogen bonds (HBs), it was recently proposed that relatively weak, isotropic van der Waals (vdW) forces are essential for understanding the properties of liquid water and ice. This insight was derived from ab initio computer simulations, which provide an unbiased description of water at the atomic level and yield information on the underlying molecular forces. However, the high computational cost of such simulations prevents the systematic investigation of the influence of vdW forces on the thermodynamic anomalies of water. Here, we develop efficient ab initio-quality neural network potentials and use them to demonstrate that vdW interactions are crucial for the formation of water's density maximum and its negative volume of melting. Both phenomena can be explained by the flexibility of the HB network, which is the result of a delicate balance of weak vdW forces, causing, e.g., a pronounced expansion of the second solvation shell upon cooling that induces the density maximum.

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