We model non-equilibrium electron transfer within a single molecule (two ferrocene units linked by a naphthalene linker) under the driving by an oscillating probe of an atomic force microscope. The model enables us to discuss the interplay of the environmental reorganization with the electron transfer process, especially the role of the relative time-scale of this process with respect to the time-scale of the electron transfer. Experimentally measured electron transfer rates show only a mild dependence on temperature, at odds with a straightforward application of the canonical detail balance condition. We explain the breakdown of the canonical detailed balance by the non-equilibrium nature of the steady state into which the system is driven by the probe. Comparison between the theory and the experiments hints at the non-equilibrium state of both the electron and at least some of the environmental degrees of freedom. However, a very good agreement can be obtained already with the model of an equilibrium environment. The non-equilibrium character of the electronic state remains crucial for the explanation of the experimental observations.
Seminar on 25 April 2019
Institute of Physics, FMP CU
Modeling of atomic force microscopy control of single molecule electron transfer
at 13:00 in Seminar room F052