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Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

preprint
revised on 31.03.2020 and posted on 02.04.2020 by Wallace Derricotte, Huiet Joseph
The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol-1. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.

Funding

Research Initiation Award: A Symmetry-Adapted Perturbation Theory Approach to Reaction Force Analysis

Directorate for Education & Human Resources

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History

Email Address of Submitting Author

wallace.derricotte@morehouse.edu

Institution

Morehouse College

Country

United States

ORCID For Submitting Author

0000-0001-5709-5168

Declaration of Conflict of Interest

no conflict of interest

Version Notes

Initial Draft for Submission

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