Electrolysis and surface phenomena. To the bicentenary of Volta’s publication on the first direct-current source
A.N. Frumkin Institute of Electrochemistry, Russian Academy of Sciences, Leninsky prosp. 31, korp. 5, Moscow, 119071, Russian Federation
The development of knowledge about electric current, potential, and the conversion of energy at the interface between electronic- and ionic-conductivity phases is briefly reviewed. Although soon after its discovery it was realized that electric current is the motion of charged particles, the double-layer field promoting charge transfer through the interface was considered for a long time to be as uniform as in a capacitor. One-dimensional ion discharge theory failed to explain the observed dependence of the current on the potential jump across the interface. The spatial segmentation of energy in the double layer due to the quantum evolution of the layer’s periphery puts a limit on the charge transfer work the field may perform locally, and creates conditions for the ionic atmosphere being spontaneously compressed after the critical potential jump has been reached. A discrete interchange of states also occurs due to the adsorption of discharged particles and corresponds to the consecutive exclusion of the d-wave function nodes of metal surface atoms, the exclusion manifesting itself in the larger longitudinal and smaller lateral sizes of the atomic orbital. The elastic extension of the metal surface reduces the d-function overlap thus intensifying adsorption. Advances in experimentation, in particular new techniques capable of detecting alternating surface tension of solids, enabled these and some other phenomena to be observed.