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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