A model multidimensional analytic potential energy function for the Cl- + CH3Br → ClCH3 + Br- reaction

Haobin Wang, Ling Zhu, William L. Hase

Research output: Contribution to journalArticle

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Abstract

Hartree-Fock calculations, utilizing the SV4PP split valence contracted Gaussian basis set for Cl and Br and the 6-31G* basis set for CH3, are used to determine potential energy surface properties for the Cl- + CH3Br → ClCH3 + Br- SN2 nucleophilic substitution reaction. This ab initio information is used in concert with experimental data to develop a multidimensional analytic potential energy function for the Cl- + CH3Br reaction system, by modifying the analytic potential energy function developed previously for Cla- + CH3Clb → ClaCH3 + Clb-. Each atom and degree of freedom is treated explicitly in the analytic function. Transition-state theory calculations are performed with the derived analytic potential to determine rate constants for Cl- + CH3Br → Cl-⋯CH3Br association, and for dissociation of the Cl-⋯CH3Br prereaction complex to reactants Cl- + CH3Br, and isomerization of this complex to the postreaction complex ClCH3⋯Br-. RRKM calculations are also performed to determine rate constants for dissociation and isomerization of the complexes versus energy and angular momentum. The analytic function developed here for the Cl- + CH3Br → ClCH3 + Br- system has been incorporated into the general chemical dynamics computer program VENUS.

Original languageEnglish
Pages (from-to)1608-1619
Number of pages12
JournalJournal of Physial Chemistry
Volume98
Issue number6
DOIs
StatePublished - 1994

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