Nonadiabatic charge transfer process

Emission of charged particles exoelectron) [11, 12] and light chemiluminescence) [13-15] during gas adsorption or reaction is generally attributed to a nonadiabatic charge transfer process. 

Khoshtariya D. E., Dolidze T. D., Zusman L. D. and Waldeck D. H. (2001), Observation of the turnover between the solvent friction (overdamped) and tunneling (nonadiabatic) charge-transfer mechanisms for a Au/Fe(CN)6 " electrode process and evidence for a freezing out of the Marcus barrier , J. Phys. Chem. Alas, 1818-1829. 

A number of different approaches may be subsumed under this heading—approaches which are not restricted to nonadiabatic reactions. In remote encounters, the initial and final states refer to separated reactants and products, respectively, and the transition probability may be computed from the corresponding energy defect this model is familiar for charge-transfer processes, but has been applied to chemical reactions. The effect of spin and symmetry conservation on such crossings has also been assessed qualitatively. The importance of the Franck-Condon overlap integral in determining the transition probability has also been treated semiempirically. In the theoretical discussion of nonadiabatic reactions, it is standard practice to compute the transition probability between the surfaces, for example, by Landau-Zener theory. ... 

Understanding the theoretical principles of light induced nonadiabatic reactions is therefore crucial for the comprehension of the photo-driven processes that lead to photoinduced charge transfer and energy transfer reactions which will be discussed later on in this thesis. 

Charge injection is fast compared with nuclear relaxation of the excited state (k k,). In this case, interfacial charge transfer would take place from the prepared hot vibronic level (Eq. (34)) and the quantum yield for the primary injection process would be close to unity = 1). For both limiting cases, k[ kr and k[ kr, relation (30) would be relevant, provided electron transfer is nonadiabatic. 

The dynamical processes can be investigated in two different ways the adiabatic processes, where the system remains in the electronic ground state and the nonadiabatic processes where electronic excitation, ionization or charge transfer occur. Only the ways to study adiabatic phenoma will be described here. 

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