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Direct-dynamics VTST study of hydrogen or deuterium abstraction and C–C bond formation or dissociation in the reactions of CH

_{3} + CH

_{4}, CH

_{3} + CD

_{4}, CH

_{3}D + CD

_{3}, CH

_{3}CH

_{3} + H, and CH

_{3}CD

_{3} + D

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10.1063/1.4803862

### Abstract

Direct-dynamics variational transition-state theory calculations are studied at the MPWB1K/6-311++G(d,p) level for the four parts of reactions. The first part is hydrogen or deuterium abstraction in the reactions of CH3 + CH4, CH3 + CD4, and CH3D + CH3. The second part involves C–C bond formation in these reactions. The third one is the reactions of CH3CH3 + H and CH3CD3 + D to form of H2, HD, and D2. The last one is the dissociation of C–C bonds in the last group of reactions. The ground-state vibrational adiabatic potential is plotted for all channels. We have carried out direct-dynamics calculations of the rate constants, including multidimensional tunneling in the temperature range T = 200–2200 K. The results of CVT/μOMT rate constants were in good agreement with the experimental data which were available for some reactions. Small-curvature tunneling and Large-curvature tunneling with the LCG4 version were used to include the quantum effects in calculation of the rate constants. To try to find the region of formation and dissociation of bounds we have also reported the variations of harmonic vibrational frequencies along the reaction path. The thermally averaged transmission probability (P(E)exp (−ΔE/RT)) and representative tunneling energy at 298 K are reported for the reactions in which tunneling is important. We have calculated kinetic isotope effect which shows tunneling and vibrational contributions are noticeable to determine the rate constant. Nonlinear least-squares fitting is used to calculate rate constant expressions in the temperature range 200–2200 K. These expressions revealed that pre-exponential factor includes two parts; the first part is a constant number which is important at low temperatures while the second part is temperature dependent which is significant at high temperatures.

© 2013 AIP Publishing LLC

Received 23 May 2011
Accepted 22 April 2013
Published online 20 May 2013

Article outline:

I. INTRODUCTION

II. METHOD

A. *Ab initio* calculations

B. Dynamics calculations

III. RESULTS AND DISCUSSION

A. H/D abstraction reactions ((R1), (R5)–(R7))

B. S_{N}2 reactions ((R2) and (R8)–(R10))

C. H/D abstraction by H or D radicals ((R3), (R11), and (R12))

D. CH_{3}/CD_{3} abstraction by H or D radicals ((R4), (R13), and (R14))

IV. CONCLUSION

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2013-05-20

2014-04-18

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