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: kinetic processes, activated state, polaron, spin polaron
Full text
PDF



Selected References
These references are in PubMed. This may not be the complete list of references from this article.
- Kemeny G. Collective aspects of conformons and the electron transfer chain. J Theor Biol. 1974 Nov;48(1):231–241. doi: 10.1016/0022-5193(74)90193-3. [DOI] [PubMed] [Google Scholar]
- Kemeny G., Goklany I. M. Polarons and conformons. J Theor Biol. 1973 Jul;40(1):107–123. doi: 10.1016/0022-5193(73)90167-7. [DOI] [PubMed] [Google Scholar]
- Lumry R., Rajender S. Enthalpy-entropy compensation phenomena in water solutions of proteins and small molecules: a ubiquitous property of water. Biopolymers. 1970;9(10):1125–1227. doi: 10.1002/bip.1970.360091002. [DOI] [PubMed] [Google Scholar]
- Rosenberg B., Kemeny G., Switzer R. C., Hamilton T. C. Quantitative evidence for protein denaturation as the cause of thermal death. Nature. 1971 Aug 13;232(5311):471–473. doi: 10.1038/232471a0. [DOI] [PubMed] [Google Scholar]
