ABSTRACT
This chapter gives an analysis of the rate constant of catalytic reactions. Transfer of an electron from a donor to an acceptor via an electron orbital of a catalyst playing the role of an intermediate short-lived state for the transferrable electron is what is meant by the bridge-assisted mechanism of electron transfer reactions. The influence of the charging of the metal surface on the subsequent elementary act is similar to the electrostatic effects in homogeneous catalysis, which are possible if the catalyst C may accept or donate more than one electron. The ideas, according to which the electron density is not confined inside the sharp boundary formed by ion cores but spreads out of the metal surface to some distance. Bridge-assisted reactions in bulk solution, interaction of the electron in the localized state in the film with the vibrational subsystem or with the polarization of the medium may be weak..
