title: Thermodynamics of liquids: standard molar entropies and heat capacities of common solvents from 2PT molecular dynamics.
abstract: We validate here the Two-Phase Thermodynamics (2PT) method for calculating the standard molar entropies and heat capacities of common liquids. In 2PT, the thermodynamics of the system is related to the total density of states (DoS), obtained from the Fourier Transform of the velocity autocorrelation function. For liquids this DoS is partitioned into a diffusional component modeled as diffusion of a hard sphere gas plus a solid component for which the DoS(υ) → 0 as υ→ 0 as for a Debye solid. Thermodynamic observables are obtained by integrating the DoS with the appropriate weighting functions. In the 2PT method, two parameters are extracted from the DoS self-consistently to describe diffusional contributions: the fraction of diffusional modes, f, and DoS(0). This allows 2PT to be applied consistently and without re-parameterization to simulations of arbitrary liquids. We find that the absolute entropy of the liquid can be determined accurately from a single short MD trajectory (20 ps) after the system is equilibrated, making it orders of magnitude more efficient than commonly used perturbation and umbrella sampling methods. Here, we present the predicted standard molar entropies for fifteen common solvents evaluated from molecular dynamics simulations using the AMBER, GAFF, OPLS AA/L and Dreiding II forcefields. Overall, we find that all forcefields lead to good agreement with experimental and previous theoretical values for the entropy and very good agreement in the heat capacities. These results validate 2PT as a robust and efficient method for evaluating the thermodynamics of liquid phase systems. Indeed 2PT might provide a practical scheme to improve the intermolecular terms in forcefields by comparing directly to thermodynamic properties.
authors.affiliation: Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA 91125, USA.
authors.forename: Tod A
authors.initials: TA
authors.lastname: Pascal
authors.forename: Shiang-Tai
authors.initials: ST
authors.lastname: Lin
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
mesh_terms: D019277:Entropy; D006358:Hot Temperature; D056004:Molecular Dynamics Simulation; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D012997:Solvents