Quantum‐Theoretical Model of Adiabatic Rate Processes in Condensed Systems or at Interfaces

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Abstract
A quantum‐theoretical model of rate processes in condensed systems is developed which is capable of treating partial charge transfer phenomena and chemical bond formation. Adiabatic local potential surfaces of a reactive subsystem are subjected to a unitary transformation into species potential surfaces; the phonon‐assisted conversion of chemical species can then be calculated in the common T‐matrix framework. In numerical calculations, anharmonicity of species potential surfaces and dependences of the electronic transition element upon nuclear coordinates is allowed for. As specific application, photoelectrochemical processes on semiconductor surfaces with fractional electrons or holes are considered.