Accurate Coupled Cluster Calculations of the Reaction Barrier Heights of Two CH3 center dot + CH4 Reactions

Wim Klopper*, Rafal A. Bachorz, David P. Tew, Jorge Aguilera-Iparraguirre, Yannick Carissan, Christof Haettig

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

9 Citations (Scopus)

Abstract

We have computed barrier heights of 71.8 +/- 2.0 and 216.4 +/- 2.0 U mol(-1) for the reactions CH4 + CH3 center dot -> CH3 center dot + CH4 and CH4 + CH3 center dot -> H-center dot + C2H6, respectively, using explicitly correlated coupled cluster theory with singles and doubles combined with standard coupled cluster theory with up to connected quadruple excitations. Transition-state theory has been used to compute the respective reaction rate constants in the temperature interval of 250-1500 K. The computed rates for the reaction to ethane are orders of magnitude slower than those used in the mechanism of Norinaga and Deutschmann (Ind. Eng. Chem. Res. 2007, 46, 3547.) for the modeling of the chemical vapor deposition of pyrolytic carbon.

Original languageEnglish
Pages (from-to)11679-11684
Number of pages6
JournalJournal of Physical Chemistry A
Volume113
Issue number43
DOIs
Publication statusPublished - 29 Oct 2009

Keywords

  • ACTIVE THERMOCHEMICAL TABLES
  • ZETA BASIS-SETS
  • TRANSITION-STATE THEORY
  • VIBRATIONAL-SPECTRUM
  • CORRELATION ENERGIES
  • CORE-VALENCE
  • MANY-BODY
  • METHANE
  • IMPLEMENTATION
  • INCLUSION

Cite this

Klopper, W., Bachorz, R. A., Tew, D. P., Aguilera-Iparraguirre, J., Carissan, Y., & Haettig, C. (2009). Accurate Coupled Cluster Calculations of the Reaction Barrier Heights of Two CH3 center dot + CH4 Reactions. Journal of Physical Chemistry A, 113(43), 11679-11684. https://doi.org/10.1021/jp902753s