Two transport mechanisms are fundamental for nanoelectrochemistry: electron transfer and mass transport. The formulation of theoretical models allows to understand the role of the different species involved in the electrochemical reactions.
The electron transfer between the reactant and the nanoelectrode can be explained by the combination of various theories based on the Marcus theory.
Mass transport, that is the diffusion of the reactant molecules from the electrolyte bulk to the nanoelectrode, is influenced by the formation of a double electric layer at the electrode/electrolyte interface. At the nanoscale it is necessary to theorize a dynamic double electric layer which takes into account an overlap of the Stern layer and the diffuse layer.
Knowledge of the mechanisms involved allows to build computational models that combine the density functional theory with electron transfer theories and the dynamic double electric layer.
In the field of molecular modelling, accurate models could predict the behaviour of the system as reactants, electrolyte or electrode change.