Temperature response of the polarizable SWM4-NDP water model

TL;DR

This study investigates the temperature-dependent properties of the polarizable SWM4-NDP water model through molecular dynamics simulations, revealing discrepancies in density behavior and hydrogen bonding compared to experimental data and other models.

Contribution

It provides the first comprehensive temperature range analysis of the SWM4-NDP model, highlighting its strengths and limitations in reproducing water's thermodynamic properties.

Findings

Density maximum occurs at 200 K, below experimental value

Hydrogen-bonding and tetrahedral order resemble TIP4P/2005

Model's current parameters need refinement for accurate behavior

Abstract

Introduction of polarizability in classical molecular simulations holds the promise to increase accuracy as well as prediction power to computer modeling. To introduce polarizability in a straight-forward way one strategy is based on Drude particles: dummy atoms whose displacements mimic polarizability. In this work, molecular dynamics simulations of SWM4-NDP, a Drude-based water model, were performed for a wide range of temperatures going from 170 K to 340 K. We found that the density maximum is located far down in the supercooled region at around 200 K, roughly 80 K below the experimental value. Very long relaxation times together with a new increase in the density were found at even lower temperatures. On the other hand, both hydrogen-bond coordination up to the second solvation shell and tetrahedral order resembled very much what was found for TIP4P/2005, a very good performer at the reproduction of the density curve and other properties of bulk water in temperature space. Such a discrepancy between the density curve and the hydrogen bond propensity was not observed in other conventional water models. Our results suggest that while the simplicity of the SWM4 model is appealing, its current parametrization needs improvements in order to correctly reproduce water behavior beyond ambient conditions.