Kirkwood-Buff integrals from molecular simulation

Journal article (2019)

Authors

N. Dawass Engineering Thermodynamics - Mechanical, Maritime and Materials Engineering

P. Krüger Chiba University

S. K. Schnell Norwegian University of Science and Technology (NTNU)

Jean Marc Simon Université de Bourgogne

T.J.H. Vlugt Engineering Thermodynamics - Mechanical, Maritime and Materials Engineering

Research Group

Engineering Thermodynamics (Mechanical, Maritime and Materials Engineering) (TU Delft)

DOI: https://doi.org/10.1016/j.fluid.2018.12.027

Kirkwood-Buff theory Molecular simulations Kirkwood-Buff integrals Density fluctuations Small system method Solution theory

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http://resolver.tudelft.nl/uuid:fb9ffec6-6adc-4e6b-b885-a9708fe46243

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Published Date

2019

Language

English

Faculty

Mechanical, Maritime and Materials Engineering

Department

Process and Energy

Research Group

Engineering Thermodynamics

Abstract

The Kirkwood-Buff (KB) theory provides a rigorous framework to predict thermodynamic properties of isotropic liquids from the microscopic structure. Several thermodynamic quantities relate to KB integrals, such as partial molar volumes. KB integrals are expressed as integrals of RDFs over volume but can also be obtained from density fluctuations in the grand-canonical ensemble. Various methods have been proposed to estimate KB integrals from molecular simulation. In this work, we review the available methods to compute KB integrals from molecular simulations of finite systems, and particular attention is paid to finite-size effects. We also review various applications of KB integrals computed from simulations. These applications demonstrate the importance of computing KB integrals for relating findings of molecular simulation to macroscopic thermodynamic properties of isotropic liquids.

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