Theory of Rate Processes and the Compensation Rule
- 1 March 1975
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences
- Vol. 72 (3) , 999-1002
- https://doi.org/10.1073/pnas.72.3.999
Abstract
The rate of intermolecular charge transfer as involved in the theory of rate processes is derived for a quadratic generalization of Holstein's one-dimensional linear polaron theory. The activation energy and the activation entropy are shown to be proportional to the number of vibrational degrees of freedom associated with each molecular site. The activation entropy is found to be negative in this model, thus decreasing the reaction rate. A spin-polaron model is introduced where the electron is coupled in a specific way to N spins at each site. In this model both the activation parameters are positive and are proportional to N. Thus, the oscillator model gives a negative and the spin model gives a positive compensation temperature.Keywords
This publication has 4 references indexed in Scilit:
- Collective aspects of conformons and the electron transfer chainJournal of Theoretical Biology, 1974
- Polarons and conformonsJournal of Theoretical Biology, 1973
- Quantitative Evidence for Protein Denaturation as the Cause of Thermal DeathNature, 1971
- Enthalpy–entropy compensation phenomena in water solutions of proteins and small molecules: A ubiquitous properly of waterBiopolymers, 1970