Marcus-Hush formalism

The analysis of the kinetics of the charge transfer is presented in Sect. 1.7 for the Butler-Volmer and Marcus-Hush formalisms, and in the latter, the extension to the Marcus-Hush-Chidsey model and a discussion on the adiabatic character of the charge transfer process are also included. The presence of mass transport and its influence on the current-potential response are discussed in Sect. 1.8. 

The Marcus-Hush (MH) formalism is an attempt to better account for changes in the outer solvation sphere during an electron transfer process. It incorporates the... 

The energy curves in Figure 22 are closely related to the Marcus-Hush theory for electron transfer. The formalism we employ emphasizes a dipole model for the solute solvent interaction, i.e., an Onsager cavity model. However, a Born charge model based on ion solvation as something in between [135] would be essentially equivalent because we do not attempt to calculate Bop and Bor but rather determine them empirically. 

In long distance ET, the presence of a wave function in the medium between donor and acceptor is the only means for donor and acceptor to communicate. The nature of this connection is expected to influence the reaction rates for ET or EET between the subsystems. Partitioning technique together with the Marcus-Hush model [6,7] may be viewed as an adaptation to practical chemistry of a full quantum mechanical treatment [21], where nuclei and electrons are treated as equal partners. In particular the influence on ET from the medium between the redox centres is formalized. 

The model developed by Marcus and Hush assumes the transition state formalism... 

The formal development of the topic will rest on a model Hamiltonian proposed by one of us in the 1980s. From this we will first derive the Levich and Dogonadze theory (5), which was the first quantum theory for electron transfer in condensed media, and then obtain the classical potential-energy surfaces that are generalizations of those famihar with Marcus and Hush. 

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