Ab Initio Quantum-Chemical Calculations in Electrochemistry

Challenge of the discharge of a hydronium ion at a mercury electrode: Beyond the Tafel plots

“…Since the rigorous quantitative description of the electrochemical hydrogen evolution at microscopic level remains a challenging and immensely complex problem (see, for example, Ref. [39]), our model should be employed first of all to clarify qualitative kinetic effects observed in experiment.…”

A Unifying View of Computational Electrochemistry

“…At present, the continuum theory-based computations remain important, and even more authors declare the keyword "Computational Electrochemistry" in their publications on such subjects (see, e.g. Out of many examples, I would mention the attempts to calculate ab initio redox potentials of electrode reactions [14][15][16], or the efforts to compute ab initio the equilibrium states and dynamic properties of intermediates of electrode processes [17]. Their work is also consistent with the research programme suggested in my paper [1].…”

First principles study of halogens adsorption on intermetallic surfaces

“…Sellers et al [38] reported that a simple thermodynamic cycle can be used to convert the binding energy of adsorbed halogen to the binding energy of halide ion and vice versa. Besides, the trends in binding energies of halides and halogens are often found to be identical [39]. Doll et al [40] studied the adsorption of chlorine on the Ag (111) surface with full potential gradient corrected density functional calculations.…”

“…The authors demonstrated that higher work function surfaces are associated with more covalent bonding, while established periodic trends in bond ionicities and metal-halogen vibrational frequencies indicate that metal-halogen bonding in vacuum interrelates with metal electrode-halogen bonding in electrochemical environment. Therefore, we prefer to study the halogen adsorption case instead of halide ion adsorption, since such a charge-neutral situation may be conveniently linked to the scale of electrochemical potentials by means of the potential of zero charge [39].…”