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Elekrrochemie J Liisungen 1 Quantenmechunik J Reulitioriskine!ik / Wellenfunktionen A theory of electron transfer processes in solution, including electrode reactions, is presented which rests on a general quantummechanical formulation of chemical kinetics. The familiar harmonic oscillator model is used to account for the role of the polar solvcnt in the electron transfer. An independent evaluation of the probabilities of electron and nuclear transitions permits to avoid the 1imit;itions of previous classical (or semiclassical) theories and that of quantum-mechanical treatments based on perturbation theorq I S well. In this way the whole intermediate region between the Limits of adiabatic and nonadiahatic processes is included and nuclear tunneling at any temperature is taken into account. The main results of earlier theories are obtained as special cases in the frame of the present treatment.

A theory of the emission of electrons from metals is developed on the basis of a general integral expression for the total transmission probability of an incident electron on the potential barrier at the metal surface. This integral is expressed as a sum of three conveniently defined integrals. In this way formulas are obtained for the current density for all temperature and field conditions of practical interest. The maximum error in the calculation of the total current by this method is about 10%. This theory includes as limiting cases thermionic and field emission as well as some earlier results for the emission over a narrow intermediate range of conditions. The limits of applicability of the theory in its general form are outside those of practical importance and include temperatures from 0 to 3500 °K and fields from 0 to 108 V/cm.