Long-distance electron tunneling

There is currently much interest in electron transfer processes in metal complexes and biological material (1-16, 35). Experimental data for electron transfer rates over long distances in proteins are scarce, however, and the semi-metheme-rythrin disproportionation system appears to be a rare authentic example of slow electron transfer over distances of about 2.8 nm. Iron site and conformational changes may also attend this process and the tunneling distances from iron-coordinated histidine edges to similar positions in the adjacent irons may be reduced from the 3.0 nm value. The first-order rate constant is some 5-8 orders of magnitude smaller than those for electron transfer involving some heme proteins for which reaction distances of 1.5-2.0 nm appear established (35). 

Fig. 4.6. Schematic pattern of the tunnelling recombination of positively changed Vk centre with neutral electron centre (e.g., F centre) (a) and with oppositely charged activator atom (e.g., Tl°) (b). In the second case the Coulomb field traps Vk at long distance R n, but electron transfer itself occurs at much shorter distance.

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