Ensemble transformation in the fluctuation theory

Seishi Shimizu; Nobuyuki Matubayasi

doi:10.1016/j.physa.2021.126430

Ensemble transformation in the fluctuation theory

Seishi Shimizu^*, Nobuyuki Matubayasi

^*Corresponding author for this work

Chemistry

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

Abstract

Interactions in complex solutions that consist of multiple components can be quantified via number correlations observed within an isochoric subsystem. The fluctuation solution theory carries out a conversion between experimental data, under isobaric conditions, and the isochoric number correlations, through cumbersome thermodynamic variable transformations. In contrast, we have recently demonstrated heuristically that direct transformation of statistical variables (i.e., those variables fluctuating in statistical ensembles such as volume and particle numbers) can lead to equivalent results via simple algebra. This paper reveals the geometrical basis of fluctuation and invariants underlying the equivalence between thermodynamic and statistical variable transformations. Based on the quasi-thermodynamic fluctuation theory and the postulate that concentration and its fluctuation are invariant under ensemble transformation, we show that the thermodynamic and statistical variable transformations correspond to the change of basis on a Hessian and statistical variables, respectively, under which the quadratic form of fluctuation is invariant. Statistical variable transformation can also be used in cases when a set of experimental data do not belong to the same ensemble. When combined with the order-of-magnitude analysis, our formalism shows that the quasi-thermodynamic formalism of fluctuation at the thermodynamic limit is valid only for extensive variables and cannot be applied to intensive variables.

Original language	English
Article number	126430
Journal	Physica A: Statistical Mechanics and its Applications
Volume	585
Early online date	15 Sept 2021
DOIs	https://doi.org/10.1016/j.physa.2021.126430
Publication status	Published - 1 Jan 2022

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Cite this

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title = "Ensemble transformation in the fluctuation theory",

abstract = "Interactions in complex solutions that consist of multiple components can be quantified via number correlations observed within an isochoric subsystem. The fluctuation solution theory carries out a conversion between experimental data, under isobaric conditions, and the isochoric number correlations, through cumbersome thermodynamic variable transformations. In contrast, we have recently demonstrated heuristically that direct transformation of statistical variables (i.e., those variables fluctuating in statistical ensembles such as volume and particle numbers) can lead to equivalent results via simple algebra. This paper reveals the geometrical basis of fluctuation and invariants underlying the equivalence between thermodynamic and statistical variable transformations. Based on the quasi-thermodynamic fluctuation theory and the postulate that concentration and its fluctuation are invariant under ensemble transformation, we show that the thermodynamic and statistical variable transformations correspond to the change of basis on a Hessian and statistical variables, respectively, under which the quadratic form of fluctuation is invariant. Statistical variable transformation can also be used in cases when a set of experimental data do not belong to the same ensemble. When combined with the order-of-magnitude analysis, our formalism shows that the quasi-thermodynamic formalism of fluctuation at the thermodynamic limit is valid only for extensive variables and cannot be applied to intensive variables. ",

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