Appropriate clusterset selection for the prediction of thermodynamic properties of liquid water with QCE theory

Abstract

Evident in many physical and chemical phenomena, thermodynamics is the study of how energy is stored, transformed and transferred in a molecule or material. However, prediction of these properties with simulation techniques is a non-trivial task as several factors such as composition and intermolecular interactions come into play. While molecular dynamics and ab initio molecular dynamics are the most common techniques for the prediction of thermodynamic properties, there exists many shortcomings associated with their use. Therefore, in this work we instead apply QCE theory to predict the thermodynamic properties of liquid water. This theory assumes that a condensed phase system can be represented as a ‘mixture’ of varying sized clusters rather than as a continuum. As QCE theory relies on first-principle simulations and statistical thermodynamics to determine the thermodynamic behavior of a system, appropriate selection of clusters is a crucial step towards achieving accurate predictions. In this study, we use molecular dynamics and ab initio calculations to obtain initial configurations of 400 water clusters, W_n where n = 3 to 10 and contrast their stability using two different criteria. The role of entropy towards cluster stabilization is investigated by comparing the binding (ΔE_BIND/mol) and Gibbs free binding energy per molecule (ΔG_BIND/mol) of various W_n at 298.15 K. Initial clustersets are constructed by exploring two-, three-, four and five-combinations of clustersets using the minimum ΔG_BIND/mol structures of W_n. We also expand the ΔG_BIND/mol criteria for W_n of sizes 3 to 7 to include values larger than 0.0 kJ mol⁻¹ and smaller than 3.0 kJ mol⁻¹ as a means of improving thermodynamic predictions. 37 of the 459 resulting clustersets predicted the correct boiling point of water and its thermodynamic properties with an accuracy of 95%. A scaled population-weighted infrared spectrum was compared to experimental results to validate the composition of the top 5 clustersets. The predicted spectra showed an exact match within the low frequency range (<1000 cm⁻¹) with some discrepancy at the high frequency range (>3400 cm⁻¹). This work highlights that ΔG_BIND/mol is so far the best criteria to apply when determining an appropriate clusterset for QCE theory.