Agronomy and Horticulture Department
Date of this Version
4-25-2023
Citation
Publisheed (2023) Journal of Chemical Theory and Computation
Abstract
The description of chemical processes at the molecular level is often facilitated by use of reaction coordinates, or collective variables (CVs). The CV measures the progress of the reaction and allows the construction of profiles that track the evolution of a specific property as the reaction progresses. Whereas CVs are routinely used, especially alongside enhanced sampling techniques, links between profiles and thermodynamic state functions and reaction rate constants are not rigorously exploited. Here, we report a unified treatment of such reaction profiles. Tractable expressions are derived for the free-energy, internal-energy, and entropy profiles as functions of only the CV. We demonstrate the ability of this treatment to extract quantitative insight from the entropy and internal-energy profiles of various real-world physicochemical processes, including intramolecular organic reactions, ionic transport in superionic electrolytes, and molecular transport in nanoporous materials.
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Agricultural Science Commons, Agriculture Commons, Agronomy and Crop Sciences Commons, Botany Commons, Horticulture Commons, Other Plant Sciences Commons, Plant Biology Commons
Comments
Used by permission.