Calculating Entropies of Large Molecules in Aqueous Phase

Oliver J. Conquest; Tanglaw Roman; Aleksei Marianov; Alena Kochubei; Yijao Jiang; Catherine Stampfl

doi:10.1021/acs.jctc.1c00848

Calculating Entropies of Large Molecules in Aqueous Phase

Oliver J. Conquest, Tanglaw Roman, Aleksei Marianov, Alena Kochubei, Yijao Jiang, Catherine Stampfl

College of Science and Engineering

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

3 Citations (Scopus)

Abstract

Entropy benchmarking of different sized molecules in aqueous phase is carried out for known solvation models, where we compare geometry and solvation cavity packing parameters, which allows us to improve the accuracy of the obtained entropy values using empirical corrections. A comparison of solvation entropy models is conducted for a benchmarking set of 56 molecules, showing how an accurate description of cavitation entropy and its hindrance on other entropy values is important for large-sized solute molecules. Finally, we compare reaction free energies with entropies calculated using the most accurate solvation model considered, where we demonstrate a significant improvement in the accuracy relative to experimental values.

Original language	English
Pages (from-to)	7753-7771
Number of pages	19
Journal	Journal of Chemical Theory and Computation
Volume	17
Issue number	12
DOIs	https://doi.org/10.1021/acs.jctc.1c00848
Publication status	Published - 14 Dec 2021

Bibliographical note

Funding Information:
The authors acknowledge financial support from the Australian Research Council and The University of Sydney Nano Institute, Grand Challenge, CO Zero. They acknowledge computational support from the National Computational Infrastructure and access to computing resources. Finally, they acknowledge scientific and technical support provided by the Sydney Informatics Hub and access to the Artemis High-Performance Computing Facility at the University of Sydney. 2

Publisher Copyright:
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Keywords

Calculating Entropies
Large Molecules
Aqueous Phase

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10.1021/acs.jctc.1c00848Licence: In Copyright

Cite this

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abstract = "Entropy benchmarking of different sized molecules in aqueous phase is carried out for known solvation models, where we compare geometry and solvation cavity packing parameters, which allows us to improve the accuracy of the obtained entropy values using empirical corrections. A comparison of solvation entropy models is conducted for a benchmarking set of 56 molecules, showing how an accurate description of cavitation entropy and its hindrance on other entropy values is important for large-sized solute molecules. Finally, we compare reaction free energies with entropies calculated using the most accurate solvation model considered, where we demonstrate a significant improvement in the accuracy relative to experimental values. ",

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AU - Conquest, Oliver J.

AU - Roman, Tanglaw

AU - Marianov, Aleksei

AU - Kochubei, Alena

AU - Jiang, Yijao

AU - Stampfl, Catherine

N1 - Funding Information: The authors acknowledge financial support from the Australian Research Council and The University of Sydney Nano Institute, Grand Challenge, CO Zero. They acknowledge computational support from the National Computational Infrastructure and access to computing resources. Finally, they acknowledge scientific and technical support provided by the Sydney Informatics Hub and access to the Artemis High-Performance Computing Facility at the University of Sydney. 2 Publisher Copyright: ©

PY - 2021/12/14

Y1 - 2021/12/14

N2 - Entropy benchmarking of different sized molecules in aqueous phase is carried out for known solvation models, where we compare geometry and solvation cavity packing parameters, which allows us to improve the accuracy of the obtained entropy values using empirical corrections. A comparison of solvation entropy models is conducted for a benchmarking set of 56 molecules, showing how an accurate description of cavitation entropy and its hindrance on other entropy values is important for large-sized solute molecules. Finally, we compare reaction free energies with entropies calculated using the most accurate solvation model considered, where we demonstrate a significant improvement in the accuracy relative to experimental values.

AB - Entropy benchmarking of different sized molecules in aqueous phase is carried out for known solvation models, where we compare geometry and solvation cavity packing parameters, which allows us to improve the accuracy of the obtained entropy values using empirical corrections. A comparison of solvation entropy models is conducted for a benchmarking set of 56 molecules, showing how an accurate description of cavitation entropy and its hindrance on other entropy values is important for large-sized solute molecules. Finally, we compare reaction free energies with entropies calculated using the most accurate solvation model considered, where we demonstrate a significant improvement in the accuracy relative to experimental values.

KW - Calculating Entropies

KW - Large Molecules

KW - Aqueous Phase

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ER -

Calculating Entropies of Large Molecules in Aqueous Phase

Abstract

Bibliographical note

Keywords

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