Intramolecular electron transfer, nonadiabatic

Finally, we consider the performance of the MFT method for nonadiabatic dynamics induced by avoided crossings of the respective potential energy surfaces. We start with the discussion of the one-mode model. Model IVa, describing ultrafast intramolecular electron transfer. The comparison of the MFT method (dashed line) with the quantum-mechanical results (full line) shown in Fig. 5 demonstrates that the MFT method gives a rather good description of the short-time dynamics (up to 50 fs) for this model. For longer times, however, the dynamics is reproduced only qualitatively. Also shown is the time evolution of the diabatic electronic coherence which, too, is... 

Finally, we discuss applications of the ZPE-corrected mapping formalism to nonadiabatic dynamics induced by avoided crossings of potential energy surfaces. Figure 27 shows the diabatic and adiabatic electronic population for Model IVb, describing ultrafast intramolecular electron transfer. As for the models discussed above, it is seen that the MFT result (y = 0) underestimates the relaxation of the electronic population while the full mapping result (y = 1) predicts a too-small population at longer times. In contrast to the models... 

The nontraditional example of applying the AMSA theory is connected with the treatment of electrolyte effects in intramolecular electron transfer (ET) reactions [21, 22], Usually the process of the transfer of the electron from donor (D) to acceptor (A) in solutions is strongly nonadiabatic. The standard description of this process in connected with semiclassical Marcus theory [35], which reduces a complex dynamical problem of ET to a simple expression of electron... 

Phys. 74 6746 (1981) b) G. L. Gloss, L. T. Calcaterra, N. J. Green, K. W. Penfield, and J. R. Miller, Distance, stereoelectronic effects, and the Marcus inverted region in intramolecular electron transfer in organic radical anions, J. Phys. Chem. 90 3673 (1986). a) S. Larsson, Electron transfer in chemical and biological systems. Orbital rules for nonadiabatic transfer, J. Am. Chem. Soc. 103 4034 (1981) b) S. Larsson, n Systems as bridges for electron transfer between transition metal ions, Chem. Phys. Lett. 90 136 (1982) c) S. Larsson, Electron transfer in proteins, J. Chem. Soc., Faraday Trans. 2 79 1375 (1983) d) S. Larsson, Electron-exchange reaction in aqueous solution, J. Phys. Chem. 88 1321 (1984) e) S. Larsson,... 

Traub, M.C., Brunschwig, B.S. and Lewis, N.S. (2007) Relationships between nonadiabatic bridged intramolecular, electrochemical, and electrical electron-transfer processes./. Phys. Chem. B, 111, 6676-6683. 

This review has focused on the evaluation and analysis of the kinetic quantities primarily responsible for controlling transfer of an electron between TMC complexes, either in bimolecular processes, or in analogous intramolecular processes in which the TMCs are tethered by molecular bridging units. The primary focus is on electronic coupling elements (// f), formulated in a unified framework encompassing thermal and optical ET (i.e., for cases of both resonant and nonreson-ant D and A sites). The thermal ET treatment spans the nonadiabatic and adiabatic limits within the context of the TST. 

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