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Theoretical Study of Electron Transfer in Ferrocytochromes

Stuchebrukhov, A. A. and Marcus, R. A. (1995) Theoretical Study of Electron Transfer in Ferrocytochromes. Journal of Physical Chemistry, 99 (19). pp. 7581-7590. ISSN 0022-3654. doi:10.1021/j100019a044.

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A series of calculations is reported of the superexchange electronic matrix element between donor and acceptor states in photoinduced long-distance electron-transfer reactions in seven Ru-modified proteins: Ru(bpy)_2im-(HisX)-cyt c, where X = 33, 39, 58, 62, 66, 72, 79. Calculated results are compared with experimental data. The model used for the calculation includes a detailed description of the donor and acceptor wave functions in terms of ligand field theory. The intervening protein medium is treated within the extended Hiickel theory. It is found that the symmetry and spatial properties of the donor/acceptor wave functions impose certain selection rules on the pathways used in electron transfer. Some paths through σ bonds are not allowed due to the symmetry requirement, for example. Also, the influence of the spatial mutual orientation of the donor and acceptor orbitals in the protein on the rates of electron transfer is analyzed. It is found that there is a strong stereochemical effect in this type of reaction. The mutual orientation of the orbitals is an important factor which determines the reaction rate, in addition to such factors as distance between donor and acceptor and concrete chemical structure of the protein matrix discussed before in the literature. In the calculations, a new method of transition amplitudes is applied. The method can be used for proteins and other large systems involving several thousand atoms. Numerically, the new method reduces the calculation of the electronic coupling between donor and acceptor to the problem of finding iteratively the minimum of a multidimensional parabola, and avoids the diagonalization of the Hamiltonian matrix.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1995 American Chemical Society. Received: September 22, 1994; In Final Form: December 28, 1994. It is a pleasure to dedicate this paper to our friend Mostafa El-Sayed and to acknowledge his many contributions in physical chemistry. The financial support of the National Science Foundation and the Office of Naval Research is acknowledged. This research was also supported by a grant from the International Joint Research Program of NEDO (Japan). A.A.S. acknowledges with pleasure the startup funds provided by the Chemistry Department at UC Davis and also many useful discussions with Dr. C. Winstead at Caltech of the computational aspect of the problem considered in the present paper. The access to computational resources of the JPL-Caltech Supercomputing Project is gratefully acknowledged.
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Office of Naval Research (ONR)UNSPECIFIED
New Energy and Industrial Technology Development Organization (NEDO) (Japan)UNSPECIFIED
University of California, DavisUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20150318-105106794
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Official Citation:Theoretical Study of Electron Transfer in Ferrocytochromes A. A. Stuchebrukhov and R. A. Marcus The Journal of Physical Chemistry 1995 99 (19), 7581-7590 DOI: 10.1021/j100019a044
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55888
Deposited By: Tony Diaz
Deposited On:18 Mar 2015 19:27
Last Modified:10 Nov 2021 20:51

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