Skourtis Spiros S, Balabin Ilya A, Kawatsu Tsutomu, Beratan David N
Department of Physics, University of Cyprus, P.O. Box 20537, Nicosia 1678, Cyprus.
Proc Natl Acad Sci U S A. 2005 Mar 8;102(10):3552-7. doi: 10.1073/pnas.0409047102. Epub 2005 Feb 28.
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.
我们计算了六种钌-天青蛋白衍生物的供体-受体隧穿矩阵元<T(DA)(t)T(DA)(0)>的自相关函数。将此衰减时间与时间相关的弗兰克-康登因子的衰减时间（由罗斯基及其同事计算得出[洛克伍德，D.M.，程，Y.-K.和罗斯基，P.J.（2001年）《化学物理快报》345，159 - 165]）进行比较，揭示了非康登效应影响电子转移速率的程度。研究<T(DA)(t)T(DA)(0)>作为供体-受体距离、隧穿途径结构、隧穿能量和温度的函数，以探索非康登效应的结构和动力学起源。对于天青蛋白，相关函数对隧穿途径结构非常不敏感。衰减时间仅比小分子中溶剂介导的电子转移略短，并且主要源于价角的波动而非键长的波动。
