Shimizu, Seishi orcid.org/0000-0002-7853-1683 and Matubayasi, Nobuyuki (2020) Intensive nature of fluctuations:reconceptualizing Kirkwood-Buff theory via elementary algebra. JOURNAL OF MOLECULAR LIQUIDS. 8. ISSN 0167-7322
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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Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2020 Elsevier B.V. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 03 Sep 2020 10:00 |
Last Modified: | 16 Oct 2024 16:22 |
Published Version: | https://doi.org/10.1016/j.molliq.2020.114225 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1016/j.molliq.2020.114225 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:165094 |
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