The Quantum-mechanical Theory of an Elementary Act

Abstract

Soon after it was established that the discharge stage has a finite rate, efforts began to be made to develop a quantum-mechanical theory of an elementary act. The first important step in this direction was taken by Gurney[6]. He clearly formulated the basic idea that the transfer of an electron from a metal to an ion in solution (or in the reverse direction) can be accomplished only when the energy levels of the initial and the final states turn out to be virtually identical (for example, an electron on the Fermi level in a metal + a singly-charged ion in solution is the initial state and an electron + an ion, i.e. the atom in solution is the final state). Such an identity of energy levels for the initial and final equilibrium states can appear only as an extremely rare exception (at equilibrium free energies and not internal energies are equal, while for each elementary act the equalization of internal energies is required). According to Gurney, the equalization of energies necessary for an electron transfer is attained due to fluctuations of the polar solvent interacting with a charge.