Path-integral Monte-Carlo simulations for electronic dynamics on molecular chains: II. Transport across impurities

Physics – Condensed Matter – Mesoscale and Nanoscale Physics

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10 pages, 10 figures

Scientific paper

10.1063/1.1896355

Electron transfer (ET) across molecular chains including an impurity is studied based on a recently improved real-time path integral Monte Carlo (PIMC) approach [J. Chem. Phys. {\bf 121}, 12696 (2004)]. The reduced electronic dynamics is studied for various bridge lengths and defect site energies. By determining intersite hopping rates from PIMC simulations up to moderate times, the relaxation process in the extreme long time limit is captured within a sequential transfer model. The total transfer rate is extracted and shown to be enhanced for certain defect site energies. Further, it is revealed that the entire bridge compound approaches a steady state on a much shorter time scale than that related to the total transfer which allows for a simplified description of ET along donor-bridge-acceptor systems in the long time range.

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