The reaction of CN with CH4 and CD4: an experimental and theoretical study

D. L. Yang, T. Yu, Ming-Chang Lin, C. F. Melius*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

The kinetics of the CN reaction with CH4 and CD4 were studied by laser induced fluorescence in the temperature range of 183 to 740 K. The measured rates may effectively be expressed, in units of cm3/s, by kCH4 = 5.15 × 10-16 T1.53 exp(-504/T) and kCD4 = 8.51 × 10-19 T2.38 exp(-403/T). Both reactions increased monotopically with temperature and exhibited a significant isotope effect. Variational TST calculations were performed for these reactions in which the energies of the transition state were calculated at several points along the reaction coordinate using the BAC-MP4 method. It was determined that as the temperature was increased, the position of the transition state moved towards smaller values of the NC:HCH3(DCD3) reaction coordinates for both CH4 and CD4 reactions. This affected both the zero-point energies and entropies of reactions. Good agreement was found between the calculated and experimental activation energies of the reactions.

Original languageEnglish
Pages (from-to)271-280
Number of pages10
JournalChemical Physics
Volume177
Issue number1
DOIs
StatePublished - 1 Nov 1993

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