Protein dynamics and electron transfer: electronic decoherence and non-Condon effects |
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Authors: | Skourtis Spiros S Balabin Ilya A Kawatsu Tsutomu Beratan David N |
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Affiliation: | Department of Physics, University of Cyprus, P.O. Box 20537, Nicosia 1678, Cyprus. skourtis@ucy.ac.cy |
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Abstract: | We compute the autocorrelation function of the donor-acceptor tunneling matrix element for six Ru-azurin derivatives. Comparison of this decay time to the decay time of the time-dependent Franck-Condon factor {computed by Rossky and coworkers [Lockwood, D. M., Cheng, Y.-K. & Rossky, P. J. (2001) Chem. Phys. Lett. 345, 159-165]} reveals the extent to which non-Condon effects influence the electron-transfer rate. is studied as a function of donor-acceptor distance, tunneling pathway structure, tunneling energy, and temperature to explore the structural and dynamical origins of non-Condon effects. For azurin, the correlation function is remarkably insensitive to tunneling pathway structure. The decay time is only slightly shorter than it is for solvent-mediated electron transfer in small organic molecules and originates, largely, from fluctuations of valence angles rather than bond lengths. |
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Keywords: | correlation functions Franck-Condon breakdown dephasing coupling pathways redox reactions |
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