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Issue 11, 2018
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Generalised Marcus theory for multi-molecular delocalised charge transfer

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Abstract

Although Marcus theory is widely used to describe charge transfer in molecular systems, in its usual form it is restricted to transfer from one molecule to another. If a charge is delocalised across multiple donor molecules, this approach requires us to treat the entire donor aggregate as a unified supermolecule, leading to potentially expensive quantum-chemical calculations and making it more difficult to understand how the aggregate components contribute to the overall transfer. Here, we show that it is possible to describe charge transfer between groups of molecules in terms of the properties of the constituent molecules and couplings between them, obviating the need for expensive supermolecular calculations. We use the resulting theory to show that charge delocalisation between molecules in either the donor or acceptor aggregates can enhance the rate of charge transfer through a process we call supertransfer (or suppress it through subtransfer). The rate can also be enhanced above what is possible with a single donor and a single acceptor by judiciously tuning energy levels and reorganisation energies. We also describe bridge-mediated charge transfer between delocalised molecular aggregates. The equations of generalised Marcus theory are in closed form, providing qualitative insight into the impact of delocalisation on charge dynamics in molecular systems.

Graphical abstract: Generalised Marcus theory for multi-molecular delocalised charge transfer

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Publication details

The article was received on 05 Jan 2018, accepted on 11 Feb 2018 and first published on 13 Feb 2018


Article type: Edge Article
DOI: 10.1039/C8SC00053K
Citation: Chem. Sci., 2018,9, 2942-2951
  • Open access: Creative Commons BY license
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    Generalised Marcus theory for multi-molecular delocalised charge transfer

    N. B. Taylor and I. Kassal, Chem. Sci., 2018, 9, 2942
    DOI: 10.1039/C8SC00053K

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