SCC-DFTB-PIMD Method To Evaluate a Multidimensional Quantum Free-Energy Surface for a Proton-Transfer Reaction

The self-consistent charge density functional tight binding method was combined with the path-integral molecular dynamics method for the first time to evaluate the two-dimensional free-energy surface including nuclear quantum effects of a proton-transfer reaction in a 2,4-dichlorophenol–trimethylami...

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Bibliographic Details
Published inJournal of chemical theory and computation Vol. 15; no. 9; pp. 4965 - 4973
Main Authors Kosugi, Kento, Nakano, Hiroshi, Sato, Hirofumi
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 10.09.2019
Subjects
Charge density
Charge transfer
Hydrogen atoms
Molecular dynamics
Organic chemistry
Protons
Quantum chemistry
Trimethylamine
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Summary:The self-consistent charge density functional tight binding method was combined with the path-integral molecular dynamics method for the first time to evaluate the two-dimensional free-energy surface including nuclear quantum effects of a proton-transfer reaction in a 2,4-dichlorophenol–trimethylamine complex. A statistically converged two-dimensional quantum free-energy surface was evaluated by the multidimensional blue moon ensemble method. The accuracy was guaranteed by optimizing the repulsive potential between the sp3-hybridized nitrogen and hydrogen atoms in a SCC-DFTB3 parameter set for the system to reproduce high-level quantum chemical calculations. The present study illustrates the usefulness of this new approach to investigate nuclear quantum effects in various realistic proton-transfer reactions.
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ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.9b00355