title: Protein dynamics and electron transfer: electronic decoherence and non-Condon effects.
abstract: We compute the autocorrelation function of the donor-acceptor tunneling matrix element <T(DA)(t)T(DA)(0)> 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. <T(DA)(t)T(DA)(0)> 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.
authors.affiliation: Department of Physics, University of Cyprus, P.O. Box 20537, Nicosia 1678, Cyprus. skourtis@ucy.ac.cy
authors.forename: Spiros S
authors.initials: SS
authors.lastname: Skourtis
authors.forename: Ilya A
authors.initials: IA
authors.lastname: Balabin
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Kawatsu
authors.forename: David N
authors.initials: DN
authors.lastname: Beratan
mesh_terms: D001400:Azurin / Q000737:chemistry*; D004579:Electron Transport; D008958:Models, Molecular
chemical_list: D001400:Azurin
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