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On the microscopic kinetic theory of a chemical reaction in the limit of high collision frequency

 

作者: E. Marechal,   M. Moreau,  

 

期刊: Molecular Physics  (Taylor Available online 1984)
卷期: Volume 51, issue 1  

页码: 133-140

 

ISSN:0026-8976

 

年代: 1984

 

DOI:10.1080/00268978400100091

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

The microscopic evolution of a one parameter reaction system in a dense phase is represented, in the diffusion limit, by a Smoluchowski equation with a bistable potential. The WKB techniques recently developed are applied to the calculation of the time dependent reactive fluxk(t), defined as a derivative of the correlation function of the number of particles, in the case of a simplified model of n-butane isomerization already studied by Chandler and other authors. The reactive flux is expressed as a sum of decreasing exponentials; the larger characteristic times and corresponding numerical coefficients are computed explicitly. The results confirm the validity of the phenomenological rate law for times larger than 10-12s.

 

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