Two-dimensional free-energy surface on the exchange reaction of alkyl chloride/chloride using the QM/MM-MC method

Masayuki Ohisa, Hiroshi Yamataka, Michel Dupuis, Misako Aida

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Two-dimensional free-energy surfaces are calculated for alkyl chloride/chloride exchange/inversion reactions: Cl- + RCl (R = Me and t-Bu) surrounded by one hundred H2O molecules as a model of solvent. The methodology of free-energy calculation by perturbation theory based on a mixed-Hamiltonian model (QM/MM) combined with Monte Carlo sampling of the solvent configurations was used to obtain the changes in solvation free energy. We devised a special procedure to analyze the two-dimensional free-energy surfaces to gain unique insight into the differences in the reaction mechanisms between the two systems. The inversion reaction path for R = t-Bu on the free-energy surface is found to proceed in an asynchronous way within a concerted framework via the ion-pair region. This is in contrast to the R = Me system that proceeds as a typical SN2 reaction.

Original languageEnglish
Pages (from-to)844-849
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume10
Issue number6
DOIs
Publication statusPublished - 2008

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Free energy
Chlorides
free energy
chlorides
inversions
Hamiltonians
Solvation
solvation
perturbation theory
sampling
methodology
Ions
Sampling
Molecules
configurations
molecules
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Two-dimensional free-energy surface on the exchange reaction of alkyl chloride/chloride using the QM/MM-MC method. / Ohisa, Masayuki; Yamataka, Hiroshi; Dupuis, Michel; Aida, Misako.

In: Physical Chemistry Chemical Physics, Vol. 10, No. 6, 2008, p. 844-849.

Research output: Contribution to journalArticle

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