Electrode double layer lateral fields

What is next Several examples were given of modem experimental electrochemical techniques used to characterize electrode-electrolyte interactions. However, we did not mention theoretical methods used for the same purpose. Computer simulations of the dynamic processes occurring in the double layer are found abundantly in the literature of electrochemistry. Examples of topics explored in this area are investigation of lateral adsorbate-adsorbate interactions by the formulation of lattice-gas models and their solution by analytical and numerical techniques (Monte Carlo simulations) [Fig. 6.107(a)] determination of potential-energy curves for metal-ion and lateral-lateral interaction by quantum-chemical studies [Fig. 6.107(b)] and calculation of the electrostatic field and potential drop across an electric double layer by molecular dynamic simulations [Fig. 6.107(c)]. 

In the first part of this century, electrochemical research was mainly devoted to the mercury electrode in an aqueous electrolyte solution. A mercury electrode has a number of advantageous properties for electrochemical research its surface can be kept clean, it has a large overpotential for hydrogen evolution and both the interfacial tension and capacitance can be measured. In his famous review [1], D. C. Grahame made the firm statement that Nearly everything one desires to know about the electrical double layer is ascertainable with mercury surfaces if it is ascertainable at all. At that time, electrochemistry was a self-contained field with a natural basis in thermodynamics and chemical kinetics. Meanwhile, the development of quantum mechanics led to considerable progress in solid-state physics and, later, to the understanding of electrostatic and electrodynamic phenomena at metal and semiconductor interfaces. 

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