Gibbs energies of activation for reacting systems with multiple reactant-state and transition-state conformations.

Ian H. Williams

doi:10.1002/poc.4312

Gibbs energies of activation for reacting systems with multiple reactant-state and transition-state conformations.

Ian H. Williams

Department of Chemistry

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Abstract

Three distinct procedures for obtaining the effective Gibbs energies of activation from computed energies for a reaction involving multiple reactant-state (RS) and transition-state (TS) conformers are shown to be equivalent. If Boltzmann-weighted average Gibbs energies for RS and TS are evaluated, then the Gibbs energy contribution from entropy of mixing of both RS and TS conformers must also be included in order to obtain the correct value for the effective Gibbs energy of activation. Application to a solvolytic reaction of 4,4’-dimethoxybenzhydrylpyridinium cation, which is shown to satisfy the Curtin-Hammett principle with rapid interconversion of RS conformers, demonstrates the use of each procedure for evaluation of the effective Gibbs energy of activation.

Original language	English
Article number	e4312
Journal	Journal of Physical Organic Chemistry
Volume	35
Issue number	11
Early online date	5 Jan 2022
DOIs	https://doi.org/10.1002/poc.4312
Publication status	Published - 30 Nov 2022

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

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10.1002/poc.4312

JPOC_multiple_conformers_submitted.PDF
This is the peer reviewed version of the following article: Williams, I. H., J Phys Org Chem 2022, e4312, which has been published in final form at https://doi.org/10.1002/poc.4312. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Submitted manuscript, 341 KBLicence: Unspecified

Cite this

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AB - Three distinct procedures for obtaining the effective Gibbs energies of activation from computed energies for a reaction involving multiple reactant-state (RS) and transition-state (TS) conformers are shown to be equivalent. If Boltzmann-weighted average Gibbs energies for RS and TS are evaluated, then the Gibbs energy contribution from entropy of mixing of both RS and TS conformers must also be included in order to obtain the correct value for the effective Gibbs energy of activation. Application to a solvolytic reaction of 4,4’-dimethoxybenzhydrylpyridinium cation, which is shown to satisfy the Curtin-Hammett principle with rapid interconversion of RS conformers, demonstrates the use of each procedure for evaluation of the effective Gibbs energy of activation.

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Gibbs energies of activation for reacting systems with multiple reactant-state and transition-state conformations.

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