Stochastic theory electron-transfer reactions

The Marcus equation for nonadiabatic electron-transfer reactions (Eq. B5.3.4), and the Forster theory that we discussed in Chap. 7 apply only to systems with weak intermolecular interactions, which we now can define more precisely as meaning that H21 lh steady-state approximation to the stochastic Liouville equation for a two-state reaction in this limit From Eqs. (BIO.1.15), (10.29a), (10.29b), and (10.30), we have... 

A most interesting recent development is the work of Augustin and Rabitz, who obtained a transition between statistical and perturbation theories for any type of collision, not only complex-forming ones. More general stochastic aspects of unimolecular reactions have been discussed by Sole and Widom. An application of a phase-space model to electronic transitions in atomic collisions has been reported, as well as a simple RRKM model for electronic to vibrational energy transfer in 0( Z)) -I- Nj collisions. ... 

The brief review of the newest results in the theory of elementary chemical processes in the condensed phase given in this chapter shows that great progress has been achieved in this field during recent years, concerning the description of both the interaction of electrons with the polar medium and with the intramolecular vibrations and the interaction of the intramolecular vibrations and other reactive modes with each other and with the dissipative subsystem (thermal bath). The rapid development of the theory of the adiabatic reactions of the transfer of heavy particles with due account of the fluctuational character of the motion of the medium in the framework of both dynamic and stochastic approaches should be mentioned. The stochastic approach is described only briefly in this chapter. The number of papers in this field is so great that their detailed review would require a separate article. 

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