Estimating Entropy of Liquids from Atom-Atom Radial Distribution Functions: Silica, Beryllium Fluoride and Water

TL;DR

This study evaluates how accurately atom-atom radial distribution functions can estimate the entropy of liquids like water, silica, and beryllium fluoride, revealing the strengths and limitations of pair correlation entropy in different regimes.

Contribution

It demonstrates the reliability of pair correlation entropy in predicting entropy anomalies and quantifies errors for ionic and molecular liquids, highlighting differences in accuracy.

Findings

Pair correlation entropy accurately predicts entropy anomalies.

Errors are within 10% for ionic melts, larger for water.

Residual multiparticle entropy correlates with tetrahedral order.

Abstract

Molecular dynamics simulations of water, liquid beryllium fluoride and silica melt are used to study the accuracy with which the entropy of ionic and molecular liquids can be estimated from atom-atom radial distribution function data. All three systems are known to display similar liquid-state thermodynamic and kinetic anomalies due to a region of anomalous excess entropy behaviour where entropy rises on isothermal compression. The pair correlation entropy is demonstrated to be sufficiently accurate that the density-temperature regime of anomalous behaviour as well as the strength of the entropy anomaly can be predicted reliably for both ionic melts as well as different rigid-body pair potentials for water. Errors in the total thermodynamic entropy for ionic melts due to the pair correlation approximation are of the order of 10% or less for most state points but can be significantly larger in the anomalous regime at very low temperatures. In the case of water, as expected given the rigid-body constraints for a molecular liquids, the pair correlation approximation causes significantly larger errors, between 20 and 30%, for most state points. Comparison of the excess entropy, Se, of ionic melts with the pair correlation entropy, S2, shows that the temperature dependence of Se is well described by T ??2=5 scaling across both the normal and anomalous regimes, unlike in the case of S2. As a function of density, the Se(rho) curves shows only a single maximum while the S2(rho) curves show both a maximum and a minimum. These differences in the behaviour of S2 and Se are due to the fact that the residual multiparticle entropy, delta(S) = Se - S2, shows a strong negative correlation with tetrahedral order in the anomalous regime.