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On the equilibrium approach to isomerization dynamics in liquids

 

作者: D. Borgis,   M. Moreau,  

 

期刊: Molecular Physics  (Taylor Available online 1986)
卷期: Volume 57, issue 1  

页码: 33-53

 

ISSN:0026-8976

 

年代: 1986

 

DOI:10.1080/00268978600100031

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Following Kramers, we describe the dynamics of an isomerization reactionA⇆Bas a diffusion process in a bistable intramolecular potential. In order to calculate the chemical relaxation timetr, we rely on a purely equilibrium approach, introduced by Chandler, and we focus on the properties of the time correlation functionC(t) = ⟨δNA(0) δNA(t)⟩, and of its derivatives. A plateau formalism permits the extraction of the long relaxation timetrfrom the short time dynamics of a molecule which starts att= 0 from the activated region betweenAand B. The calculation makes it possible to encompass in a unified way the low and high friction limits, which are usually treated differently. It involves the definition of a species specification function σA, which indicates microscopically if a molecule isAorB. Most of the time, σAis taken as a Heaviside function, although its definition should be experiment-dependent. We examine the possibility of taking a wide species specification, presenting a smooth variation in the activated region.

 

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