Kirkwood-Buff integrals: From fluctuations in finite volumes to the thermodynamic limit.

J Chem Phys

Center of Excellence PoreLab, Department of Chemistry, Faculty of Natural Sciences, NTNU - Norwegian University of Science and Technology, Trondheim, Norway.

Published: October 2022

The Kirkwood-Buff theory is a cornerstone of the statistical mechanics of liquids and solutions. It relates volume integrals over the radial distribution function, so-called Kirkwood-Buff integrals (KBIs), to particle number fluctuations and thereby to various macroscopic thermodynamic quantities such as the isothermal compressibility and partial molar volumes. Recently, the field has seen a strong revival with breakthroughs in the numerical computation of KBIs and applications to complex systems such as bio-molecules. One of the main emergent results is the possibility to use the finite volume KBIs as a tool to access finite volume thermodynamic quantities. The purpose of this Perspective is to shed new light on the latest developments and discuss future avenues.

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http://dx.doi.org/10.1063/5.0106162DOI Listing

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