Aspects of valence delocalization relevant to the kinetic properties of electron-transfer chains

 Metal clusters are ubiquitously used as electron-transfer (ET) agents in biology. Their presence raises the question of how the polynuclear nature of these systems influences ET. In an earlier study, a theoretical model was formulated to describe ET from a mixed-valence dimer to a diamagnetic acceptor. In the present work, this approach is generalized to analyze the effect of valence delocalization on the rate of ET in a larger class of donor–acceptor systems. Our results indicate that the effect of valence delocalization on ET rate depends on whether the mixed-valence (MV) state occurs in the initial or final state of the reaction and on the reaction regime (normal vs inverted) as defined by Marcus. The analysis provides a possible correlation between the rate constant for ET from CuA to heme a and the difference in the valence delocalization of the CuA centers in wild-type and mutant species of cytochrome c oxidase. We have analyzed the dependence of the electron flow through extended circuits containing MV clusters on valence delocalization. A significant effect was found in the fast ET regime where the capacity of the circuit to conduct electrons is optimally used. The possibility of controlling electron conduction by tuning valence delocalization is briefly addressed.