Modified transition state theory and negative apparent activation energies of simple metathesis reactions: Application to the reaction CH₃ + HBr + CH₄ + Br

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Article on modified transition state theory and negative apparent activation energies of simple metathesis reactions and application to the reaction CH₃ + HBr + CH₄ + Br.

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11 p.

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Krasnoperov, Lev N.; Peng, Jingping & Marshall, Paul December 18, 2006.

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Article on modified transition state theory and negative apparent activation energies of simple metathesis reactions and application to the reaction CH₃ + HBr + CH₄ + Br.

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11 p.

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Abstract: A modified transition state theory (MTST) has been developed for gas-phase reactions with “negative barriers”. The theory was applied to the reactions CH3 + HBr(DBr) → CH4(CH3D) + 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 1a), 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.

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2006 American Chemical Society.

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  • Journal of Physical Chemistry A, 2006, Washington D.C.: American Chemical Society, pp. 3110-3120

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 110
  • Issue: 9
  • Page Start: 3110
  • Page End: 3120
  • Pages: 11
  • Peer Reviewed: Yes

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  • December 18, 2006

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  • March 17, 2015, 10:38 a.m.

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Krasnoperov, Lev N.; Peng, Jingping & Marshall, Paul. Modified transition state theory and negative apparent activation energies of simple metathesis reactions: Application to the reaction CH₃ + HBr + CH₄ + Br, article, December 18, 2006; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc501392/: accessed September 25, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.