The rate coefficients of unimolecular reactions in the systems with power-law distributions

Cangtao Yin, Ran Guo and Jiulin Du

Physica A: Statistical Mechanics and its Applications, 2014, vol. 408, issue C, 85-95

Abstract: The rate coefficient formulae of unimolecular reactions are generalized to the systems with the power-law distributions based on nonextensive statistics, and the power-law rate coefficients are derived in the high and low pressure limits, respectively. The numerical analyses are made of the rate coefficients as functions of the ν-parameter, the threshold energy, the temperature and the number of degrees of freedom. We show that the new rate coefficients depend strongly on the ν-parameter different from one (thus from a Boltzmann–Gibbs distribution). Two unimolecular reactions, CH3CO→CH3+CO and CH3NC→CH3CN, are taken as application examples to calculate their power-law rate coefficients, which obtained with the ν-parameters slightly different from one can be exactly in agreement with all the experimental studies on these two reactions in the given temperature ranges.

Keywords: Reaction rate theory; Power-law distributions; Unimolecular reaction; Nonextensive statistics (search for similar items in EconPapers)
Date: 2014
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Citations: View citations in EconPapers (1)

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Persistent link: https://EconPapers.repec.org/RePEc:eee:phsmap:v:408:y:2014:i:c:p:85-95

DOI: 10.1016/j.physa.2014.04.021

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