Use of an improved ion-solvent potential-energy function to calculate the reaction rate and α-deuterium and microsolvation kinetic isotope effects for the gas-phase SN2 reaction of Cl-(H2O) with CH3Cl

Xin Gui Zhao, Da Hong Lu, Yi Ping Liu, Gillian C. Lynch, Donald G. Truhlar

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

We present calculations of the rate constants and secondary kinetic isotope effects for the gas-phase SN2 reaction Cl-(H 2O)+CH3Cl based on a new chloride-water potential-energy function that has been specifically converged for heavy-water isotope effects. The results are compared to new calculations employing five chloride-water potential-energy functions that have been developed for simulations of aqueous solutions. In all calculations the ClCH3Cl- solute intramolecular potential is taken from a previous semiglobal fit to ab initio calculations including electron correlation. We also examine two different intramolecular water potentials, and we examine the effect of treating the CH3 internal rotation at the ClCH3Cl-(H 2O) transition state as a hindered rotation. Both the CH 3/CD3 (α-deuterium) and H2O/D 2O (microsolvation) kinetic isotope effects are studied.

Original languageEnglish (US)
Pages (from-to)6369-6383
Number of pages15
JournalThe Journal of Chemical Physics
Volume97
Issue number9
StatePublished - 1992
Externally publishedYes

Fingerprint

Potential energy functions
Deuterium
Isotopes
isotope effect
Reaction rates
deuterium
reaction kinetics
Gases
potential energy
Ions
vapor phases
Kinetics
kinetics
Water
Chlorides
ions
chlorides
water
Deuterium Oxide
Electron correlations

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Use of an improved ion-solvent potential-energy function to calculate the reaction rate and α-deuterium and microsolvation kinetic isotope effects for the gas-phase SN2 reaction of Cl-(H2O) with CH3Cl. / Zhao, Xin Gui; Lu, Da Hong; Liu, Yi Ping; Lynch, Gillian C.; Truhlar, Donald G.

In: The Journal of Chemical Physics, Vol. 97, No. 9, 1992, p. 6369-6383.

Research output: Contribution to journalArticle

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AU - Lu, Da Hong

AU - Liu, Yi Ping

AU - Lynch, Gillian C.

AU - Truhlar, Donald G.

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AB - We present calculations of the rate constants and secondary kinetic isotope effects for the gas-phase SN2 reaction Cl-(H 2O)+CH3Cl based on a new chloride-water potential-energy function that has been specifically converged for heavy-water isotope effects. The results are compared to new calculations employing five chloride-water potential-energy functions that have been developed for simulations of aqueous solutions. In all calculations the ClCH3Cl- solute intramolecular potential is taken from a previous semiglobal fit to ab initio calculations including electron correlation. We also examine two different intramolecular water potentials, and we examine the effect of treating the CH3 internal rotation at the ClCH3Cl-(H 2O) transition state as a hindered rotation. Both the CH 3/CD3 (α-deuterium) and H2O/D 2O (microsolvation) kinetic isotope effects are studied.

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