Surface electron screening theory and its applications to metal-electrolyte interfaces

• Published in: Progress in surface science 1986, Vol.23 (1), p.3-154
• Main Authors: Feldman, V.J., Partenskii, M.B., Vorob'ev, M.M.
• Format: Article
• Language: English
• Subjects: Chemistry; Electrochemistry; Electrodes: preparations and properties; Exact sciences and technology; General and physical chemistry; Ion selective electrodes; Miscellaneous; Other electrodes; Study of interfaces
• ISSN: 0079-6816; 1878-4240
• DOI: 10.1016/0079-6816(86)90010-9

The modern theory of the static electron response of a metal surface is reviewed. The basic motive of the survey, originated from the analysis of the contradictions between the widely accepted sharp boundary models and experiment, is self-consistency. Applications of the various versions of the density functional formalism to the surface response calculations are considered. In particular, the screening of the uniform electrostatic field is discussed on the basis of the local (Thomas-Fermi type) and nonlocal statistical models, within the Kohn-Sham scheme (in the linear response approximation and beyond it) and using sum rules. The results of the self-consistent analysis of a number of phenomena at the metal-vacuum interphase (e.g. electron and ion field emission or ionization and polarization of a minute metal particle) are briefly described. The main attention is given to the effect of a metal on the electrical properties ( the bilayer capacity first of all) of the metal-electrolyte interphases. The results obtained in this field aggravated the question about the possibility of the negative capacity values, sharply arised in connection with the “Cooper-Harrison catastrophe”. This question and the associated problem of the bilayer instability are discussed in the survey applying the results to the model microscopical calculations and the “gedanken experiments” with the electro-mechanical “catastrophe machines”.