Effects of initial state preparation on the distance dependence of electron transfer through molecular bridges and wires

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Abstract
The dependence of electron transfer rates and yields in bridged molecular systems on the bridge length, and the dependence of the zero-bias conduction of molecular wires on wire length are discussed. Both phenomena are controlled by tunneling across the molecular bridge and are consequently expected to show exponential decrease with bridge length that is indeed often observed. Deviations from this exponential dependence for long bridges, in particular a crossover to a very weak dependence on bridge length, were recently observed experimentally and discussed theoretically in terms of thermal relaxation and dephasing on the bridge. Here we discuss two other factors that potentially affect the bridge length dependence of these phenomena. First, in experiments initiated by an initial preparation of a nonstationary “donor” state the initial energy is not well defined. A small contribution from initially populated eigenstates that are of mostly bridge-level character may dominate transmission for long bridges, resulting in weak or no bridge-length dependence. Second, in steady state experiments the distribution of initial states (for example, the Fermi distribution at the electrodes in conduction experiments) will cause deviations from exponential dependence on wire length because even a small population in higher energy states will dominate the transmission through long wires. For the first scenario we show that the crossover behavior observed for electron transfer in DNA between G and GGG species separated by AT chains can be largely reproduced just by initial state effects.