Liquid–liquid criticality in the WAIL water model

Author:

Weis Jack1,Sciortino Francesco2ORCID,Panagiotopoulos Athanassios Z.1ORCID,Debenedetti Pablo G.1ORCID

Affiliation:

1. Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA

2. Department of Physics, Sapienza University of Rome, Piazzale Aldo Moro 2, I-00185 Roma, Italy

Abstract

The hypothesis that the anomalous behavior of liquid water is related to the existence of a second critical point in deeply supercooled states has long been the subject of intense debate. Recent, sophisticated experiments designed to observe the transformation between the two subcritical liquids on nano- and microsecond time scales, along with demanding numerical simulations based on classical (rigid) models parameterized to reproduce thermodynamic properties of water, have provided support to this hypothesis. A stronger numerical proof requires demonstrating that the critical point, which occurs at temperatures and pressures far from those at which the models were optimized, is robust with respect to model parameterization, specifically with respect to incorporating additional physical effects. Here, we show that a liquid–liquid critical point can be rigorously located also in the WAIL model of water [Pinnick et al., J. Chem. Phys. 137, 014510 (2012)], a model parameterized using ab initio calculations only. The model incorporates two features not present in many previously studied water models: It is both flexible and polarizable, properties which can significantly influence the phase behavior of water. The observation of the critical point in a model in which the water–water interaction is estimated using only quantum ab initio calculations provides strong support to the viewpoint according to which the existence of two distinct liquids is a robust feature in the free energy landscape of supercooled water.

Funder

National Science Foundation

Ministero dell’Istruzione, dell’Università e della Ricerca

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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