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

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

doi:10.1016/0301-0104(93)80195-F

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

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

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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 k_CH₄ = 5.15 × 10^-16 T^1.53 exp(-504/T) and k_CD₄ = 8.51 × 10^-19 T^2.38 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 language	English
Pages (from-to)	271-280
Number of pages	10
Journal	Chemical Physics
Volume	177
Issue number	1
DOIs	https://doi.org/10.1016/0301-0104(93)80195-F
State	Published - 1 Nov 1993

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title = "The reaction of CN with CH4 and CD4: an experimental and theoretical study",

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.",

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T1 - The reaction of CN with CH4 and CD4

T2 - an experimental and theoretical study

AU - Yang, D. L.

AU - Yu, T.

AU - Lin, Ming-Chang

AU - Melius, C. F.

PY - 1993/11/1

Y1 - 1993/11/1

N2 - 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.

AB - 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.

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

Abstract

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