Symmetry properties of adiabatic free energy surfaces and a diagram of kinetic modes in the case of electrochemical tunneling microscopy of redox systems

摘要

The symmetry properties of adiabatic free energy surfaces, which describe redox and dissociative electron transfer reactions in systems of the type in situ STM, are investigated. A notion of an effective overvoltage, which is a generalization of a traditional overvoltage to the case where the bias voltage is other than zero, is introduced. Diagrams of kinetic modes, which describe processes that can occur in systems of the type in situ STM under consideration, are constructed in the space of model parameters. It is shown that, in some cases, with the bias voltage other than zero, there may emerge DKR of a sufficiently complicated structure with several critical regions.