Capillary waves at the liquid-vapor interface and the surface tension of water models

TL;DR

This study uses molecular dynamics simulations to analyze capillary waves and compare the surface tension of various water models, finding that all models underestimate surface tension with TIP4P-Ew being most accurate.

Contribution

It provides a comparative analysis of surface tension predictions from different water models using capillary wave theory and thermodynamic methods.

Findings

All models underestimate surface tension.

TIP4P-Ew model best matches experimental data.

Surface tension estimates depend on the density profile fitting method.

Abstract

Capillary waves occurring at the liquid-vapor interface of water are studied using molecular dynamics simulations. In addition, the surface tension, determined thermodynamically from the difference in the normal and tangential pressure at the liquid-vapor interface, is compared for a number of standard three- and four-point water models. We study four three-point models (SPC/E, TIP3P, TIP3P-CHARMM, and TIP3P-Ew) and two four-point models (TIP4P and TIP4P-Ew). All of the models examined underestimate the surface tension; the TIP4P-Ew model comes closest to reproducing the experimental data. The surface tension can also be determined from the amplitude of capillary waves at the liquid-vapor interface by varying the surface area of the interface. The surface tensions determined from the amplitude of the logarithmic divergence of the capillary interfacial width and from the traditional thermodynamic method agree only if the density profile is fitted to an error function instead of a hyperbolic tangent function.