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By C. S Barrett
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E. Michel-Beyerle, Biophys. J. 71, A8 (1997); see also M. Bixon and J. Jortner, [11]). The activationless behavior (upper curve) corresponds to the wild-type reaction center while crossing from super-exchenge at low temperature to activated behavior at higher T is exhibited in a chemically engineered reaction center in which the bacteriochlorophyl is replaced by vinyl bacteriochlorophyl Fig. 6. Temperature dependence of the current through 1-nitro-2,5-di (phenylethynyl- 4’ -mercapto) benzene molecules between gold electrodes, showing transition from non-activated to activated behavior with a bias-dependent activation energy (After [70]) Foundations of Molecular Electronics – Charge Transport 29 Fig.
Geometric Behavior Modifications in structure lead to modifications in molecular properties; such structure/function relationships are at the heart of modern chemistry. In JC, as already stated several times, the geometries are effectively unknown, and indeed there does not seem any direct scattering method that can be used experimentally to find accurately the geometry of a molecule made of first row atoms in the presence of a large number of metal or semiconductor atoms constituting the electrode.
Until such geometric information permits comparison with computations both of the structure and of transport with different structures, this will comprise a very serious difficulty for accurate comparison between modeling and experiments. Beautiful experiments have demonstrated that electronic currents in junctions can actually break chemical bonds, excite vibrations, and otherwise alter the structural chemistry of the molecules of these junctions [53, 54, 57, 59–61, 74]. Understanding that variation remains a major task.