Intensive nature of fluctuations: reconceptualizing Kirkwood-Buff theory via elementary algebra

Seishi Shimizu; Nobuyuki Matubayasi

doi:10.1016/j.molliq.2020.114225

Intensive nature of fluctuations: reconceptualizing Kirkwood-Buff theory via elementary algebra

Seishi Shimizu, Nobuyuki Matubayasi

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Quantifying the role of solvation in soft matter and complex solutions has been made challenging by the fluctuational nature of solvation, as well as by the tedious calculus associated with it in converting thermodynamic variables. A new algebraic approach to fluctuation proposed here eliminates the tedious calculus, demonstrated by a simple rederivation of the Kirkwood-Buff theory of solutions, as well as by the calculation of higher-order fluctuations in inhomogeneous solutions. This new approach is based on a new physical insight into fluctuation in solution; concentration fluctuation, since it is independent of system size, is an invariant under transformation between ensembles, with different expressions depending on the choice of extensive variables. This is because a full set of intensive thermodynamic quantities can be represented in multiple yet equivalent ways.

Original language	English
Article number	8
Number of pages	114225
Journal	JOURNAL OF MOLECULAR LIQUIDS
Volume	318
Early online date	5 Sept 2020
DOIs	https://doi.org/10.1016/j.molliq.2020.114225
Publication status	Published - 15 Nov 2020

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10.1016/j.molliq.2020.114225

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Cite this

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title = "Intensive nature of fluctuations: reconceptualizing Kirkwood-Buff theory via elementary algebra",

abstract = "Quantifying the role of solvation in soft matter and complex solutions has been made challenging by the fluctuational nature of solvation, as well as by the tedious calculus associated with it in converting thermodynamic variables. A new algebraic approach to fluctuation proposed here eliminates the tedious calculus, demonstrated by a simple rederivation of the Kirkwood-Buff theory of solutions, as well as by the calculation of higher-order fluctuations in inhomogeneous solutions. This new approach is based on a new physical insight into fluctuation in solution; concentration fluctuation, since it is independent of system size, is an invariant under transformation between ensembles, with different expressions depending on the choice of extensive variables. This is because a full set of intensive thermodynamic quantities can be represented in multiple yet equivalent ways. ",

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