Protein dynamics and electron transfer: electronic decoherence and non-Condon effects.


Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Skourtis, SS; Balabin, IA; Kawatsu, T; Beratan, DN

Published Date

  • March 2005

Published In

Volume / Issue

  • 102 / 10

Start / End Page

  • 3552 - 3557

PubMed ID

  • 15738409

Pubmed Central ID

  • 15738409

Electronic International Standard Serial Number (EISSN)

  • 1091-6490

International Standard Serial Number (ISSN)

  • 0027-8424

Digital Object Identifier (DOI)

  • 10.1073/pnas.0409047102


  • eng