Journal
JOURNAL OF MOLECULAR LIQUIDS
Volume 318, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.molliq.2020.114225
Keywords
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Funding
- Gen Foundation
- Steven Abbott TCNF Ltd.
- Japan Society for the Promotion of Science [JP19H04206]
- Elements Strategy Initiative for Catalysts and Batteries [JPMXP0112101003]
- Fugaku Supercomputing Project from the Ministry of Education, Culture, Sports, Science and Technology
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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 rederivat ion 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 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. (C) 2020 Elsevier B.V. All rights reserved.
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