Quantum Theory of Electron‐Transfer Processes in Solution

Abstract

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.

Reduction of silver complexes: towards an ever more elaborated insight in the influence of the type of ligand on the reaction rate

“…of energy levels DðEÞ [21][22][23][24][25][26][27], shown in Fig. 2 for both the oxidising and reducing agent of a redox couple as a function of the energy, and with their respective maxima at E ox and E red .…”

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