Modified transition state theory and negative apparent activation energies of simple metathesis reactions: Application to the reaction CH 3 + HBr → CH 4 + Br

Lev N. Krasnoperov, Jingping Peng, Paul Marshall

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29 Scopus citations

Abstract

A modified transition state theory (MTST) has been developed for gas-phase reactions with "negative barriers". The theory was applied to the reactions CH 3 + HBr(DBr) → CH 4(CH 3D) + Br (1a, 1b), which exhibit negative temperature dependences. Accurate ab initio calculations performed with coupled cluster theory extrapolated to the complete basis set limit revealed a transition state located at -2.3 kJ mol -1 relative to the ground state of the reactants (in reaction la), as well as a shallow bound complex. The negative temperature dependence, the absolute values of the rate constant, and the isotope substitution effect are reproduced with good accuracy (10%), without any adjustment or fitting parameters. Analytical expressions are presented for MTST including angular momentum conservation, centrifugal barriers and tunneling. This analysis uses information about the possibly loose entrance barrier and the transition state but does not invoke a statistical intermediate complex.

Original languageEnglish (US)
Pages (from-to)3110-3120
Number of pages11
JournalJournal of Physical Chemistry A
Volume110
Issue number9
DOIs
StatePublished - Mar 9 2006

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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