Response theory for random channel kinetics in complex systems. Application to lifetime distributions of active intermediates

Marcel O. Vlad, Federico Moran and John Ross

Physica A: Statistical Mechanics and its Applications, 2000, vol. 278, issue 3, 504-525

Abstract: We present a response theory for random channel kinetics, based on the method of characteristic functionals. We assume that the fluctuations of the rate coefficients are generated by the contributions of a large number of reaction channels, and can be described in terms of a set of grand canonical probability density functionals. We consider linear as well as nonlinear responses for systems with static or dynamic disorder. For all cases considered we derive analytical expressions for the ensemble average of the response of the system to an external perturbation. The theory is applied for developing a new approach to the analysis of the kinetics in complex chemical systems, based on a random channel approach. We assume that the total transition rate from one state of the system to another is made up of the contributions of a large number of random reaction pathways, which can be described in terms of a stochastic point process. We study the response of such a system to an external perturbation and show that it can be expressed in terms of a set of lifetime distributions of reaction intermediates. We examine the possibilities of applying the technique to the study of large chemical systems by means of tracer experiments and suggest methods for computing rate distributions from measured lifetime distributions. We generalize the method of spectral kinetic analysis for the interpretation of measured lifetime distributions. We investigate the relationships between spectral kinetics analysis and random channel statistics.

Date: 2000
References: View complete reference list from CitEc
Citations:

Downloads: (external link)
http://www.sciencedirect.com/science/article/pii/S0378437199005907
Full text for ScienceDirect subscribers only. Journal offers the option of making the article available online on Science direct for a fee of $3,000

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:eee:phsmap:v:278:y:2000:i:3:p:504-525

DOI: 10.1016/S0378-4371(99)00590-7

Access Statistics for this article

Physica A: Statistical Mechanics and its Applications is currently edited by K. A. Dawson, J. O. Indekeu, H.E. Stanley and C. Tsallis

More articles in Physica A: Statistical Mechanics and its Applications from Elsevier
Bibliographic data for series maintained by Catherine Liu ().