New Interfacial Bio electrochemical Electron Transfer Phenomena

The clearest results in electrochemical in situ STM of redox molecules and biomolecules are obtained when the bias voltage and the electronic broadenings are small, that is 

An additional distinction between weak and strong interactions between the redox level and the electrodes is important. In the former limit the steady-state STM process can be viewed as two consecutive, environmentally relaxed interfacial single-ET steps, each analogous to electrochemical ET (Section 2.2). This gives the steady-state tunneling current 

Imaging of Single Biomolecules by Scanning Tunneling Microscopy 

These forms are equivalent to the interfacial electrochemical ET rate constants (Eqs. (2.2) and (2.3)). Thus is the rate constant for ET from the reduced molecule to the substrate and k / the rate constant for ET from the tip to the oxidized molecule. The parameter represents the potential drop between the electrode and the solution. In the tunneling gap with approximately the same spatial extension as the electrochemical double layer(s), and /cannot, however, be regarded as independent but are correlated as [48-50, 60] 

A different scenario emerges in the opposite hmit of strong electronic interactions. Equations (2.9a)-(2.9c) are then replaced by 

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