Protein dynamics and electron transfer: electronic decoherence and non-Condon effects.
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.
Skourtis
Spiros S
SS
Department of Physics, University of Cyprus, P.O. Box 20537, Nicosia 1678, Cyprus. skourtis@ucy.ac.cy
Balabin
Ilya A
IA
Kawatsu
Tsutomu
T
Beratan
David N
DN
D001400:Azurin / Q000737:chemistry*; D004579:Electron Transport; D008958:Models, Molecular
D001400:Azurin
Acta Crystallogr D Biol Crystallogr. 1999 Feb;55(Pt 2):379-85
10089343
Proc Natl Acad Sci U S A. 2000 Feb 1;97(3):1068-72
10655485
Proc Natl Acad Sci U S A. 2000 Aug 29;97(18):9849-54
10954730
Science. 2000 Oct 6;290(5489):114-7
11021791
Annu Rev Phys Chem. 2001;52:681-750
11326078
J Am Chem Soc. 2001 Apr 4;123(13):3181-2
11457048
J Am Chem Soc. 2001 Aug 15;123(32):7877-86
11493061
Annu Rev Biophys Biomol Struct. 1992;21:349-77
1326356
J Am Chem Soc. 2004 Feb 25;126(7):2215-24
14971957
Biophys J. 2004 Mar;86(3):1813-9
14990507
Q Rev Biophys. 2003 Aug;36(3):341-72
15029828
Biochim Biophys Acta. 2004 Apr 12;1655(1-3):59-63
15100017
Photosynth Res. 1989 Jan;22(1):15-27
24424675
J Phys Chem B. 1998 Apr 30;102(18):3586-616
24889800
Science. 1995 Jun 23;268(5218):1733-5
7792598
Annu Rev Biochem. 1996;65:537-61
8811189
Biophys J. 1997 Jan;72(1):5-17
8994588
Proc Natl Acad Sci U S A. 1997 Apr 15;94(8):3703-8
9108041
Chem Biol. 1995 Jul;2(7):489-96
9383451