Minimum energy paths , potential calculation techniques

The kineties of eleetron-transfer reactions, which is also affected by the electrode potential and the metal-water interface, is more difficult and complex to treat than the thermodynamic aspects. While the theoretical development for electron transfer kinetics began decades ago, a practical implementation for surface reactions is still unavailable. Popular transition state-searching techniques such as the NEB method are not designed to search for minimum-energy reaction paths subject to a constant potential. Approximations that allow affordable quantum chemistry calculations to get around this limitation have been proposed, ranging from the electron affinity/ionization potential matching method to heuristic arguments based on interpolations. 

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