### Abstract

We present calculations of the rate constants and secondary kinetic isotope effects for the gas-phase S_{N}2 reaction Cl^{-}(H _{2}O)+CH_{3}Cl 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 ClCH_{3}Cl^{-} 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 CH_{3} internal rotation at the ClCH_{3}Cl^{-}(H _{2}O) transition state as a hindered rotation. Both the CH _{3}/CD_{3} (α-deuterium) and H_{2}O/D _{2}O (microsolvation) kinetic isotope effects are studied.

Original language | English (US) |
---|---|

Pages (from-to) | 6369-6383 |

Number of pages | 15 |

Journal | The Journal of Chemical Physics |

Volume | 97 |

Issue number | 9 |

State | Published - 1992 |

Externally published | Yes |

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### ASJC Scopus subject areas

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

### Cite this

_{N}2 reaction of Cl

^{-}(H

_{2}O) with CH

_{3}Cl.

*The Journal of Chemical Physics*,

*97*(9), 6369-6383.

**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 S _{N}2 reaction of Cl^{-}(H_{2}O) with CH_{3}Cl.** / Zhao, Xin Gui; Lu, Da Hong; Liu, Yi Ping; Lynch, Gillian C.; Truhlar, Donald G.

Research output: Contribution to journal › Article

_{N}2 reaction of Cl

^{-}(H

_{2}O) with CH

_{3}Cl',

*The Journal of Chemical Physics*, vol. 97, no. 9, pp. 6369-6383.

_{N}2 reaction of Cl

^{-}(H

_{2}O) with CH

_{3}Cl. The Journal of Chemical Physics. 1992;97(9):6369-6383.

}

TY - JOUR

T1 - 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

AU - Zhao, Xin Gui

AU - Lu, Da Hong

AU - Liu, Yi Ping

AU - Lynch, Gillian C.

AU - Truhlar, Donald G.

PY - 1992

Y1 - 1992

N2 - 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.

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.

UR - http://www.scopus.com/inward/record.url?scp=33846076294&partnerID=8YFLogxK

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M3 - Article

VL - 97

SP - 6369

EP - 6383

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 9

ER -