Marcus, R. A. (1996) Solvent dynamics: Modified Rice–Ramsperger–Kassel–Marcus theory. II. Vibrationally assisted case. Journal of Chemical Physics, 105 (13). pp. 5446-5454. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:MARjcp96
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Expressions are given for a solvent dynamics-modified Rice–Ramsperger–Kassel–Marcus (RRKM) theory for clusters. The role of vibrational assistance across the transition state region is included. The usual differential equation for motion along the slow coordinate X in constant temperature systems is modified so as to apply to microcanonical systems. A negative entropy term, –Sv(X), replaces the (1/T)∂U/∂X or (1/T)∂G/∂X which appears in canonical systems. Expressions are obtained for the RRKM-type rate constant k(X) and for the Sv(X) which appear in the differential equation. An approximate solution for steady-state conditions is given for the case that the "reaction window" is narrow. The solution then takes on a simple functional form. The validity of the assumption can be checked a posteriori. Recrossings of the transition state are included and the condition under which the treatment approaches that in Part I is described.
|Additional Information:||© 1996 American Institute of Physics. Received 21 March 1996; accepted 27 June 1996. It is a pleasure to acknowledge the support of the National Science Foundation and the Office of Naval Research in the support of this research, and to thank a reviewer for thoughtful comments.|
|Subject Keywords:||ACTIVATED-RATE-PROCESSES; ELECTRON-TRANSFER REACTIONS; TRANSITION-STATE THEORY; FREQUENCY-DEPENDENT FRICTION; DIFFUSION-CONTROLLED REACTIONS; SLOW CONFORMATIONAL-CHANGES; CHEMICAL-REACTION DYNAMICS; NON-DEBYE SOLVENTS; NONEQUILIBRIUM SOLVATION; REACTION COORDINATE|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||02 Jul 2008|
|Last Modified:||26 Dec 2012 10:08|
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