Single-Molecule Measurements Spatially Probe States Involved in Electron Transfer from CdSe/CdS Core/Shell Nanorods
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Date
2021-09-16
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Morin, Rachel M. et al.; Single-Molecule Measurements Spatially Probe States Involved in Electron Transfer from CdSe/CdS Core/Shell Nanorods; The Journal of Physical Chemistry C, 125, 38, 21246–21253, 16 September, 2021; https://doi.org/10.1021/acs.jpcc.1c06581
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This work was written as part of one of the author's official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance with 17 U.S.C. 105, no copyright protection is available for such works under U.S. Law.
Public Domain Mark 1.0
This work was written as part of one of the author's official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance with 17 U.S.C. 105, no copyright protection is available for such works under U.S. Law.
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Abstract
Semiconductor nanorods with charge-accepting molecules adsorbed on their surfaces serve as model systems for solar energy conversion. An electron photoexcited from the valence band of the nanorod to a high-energy state in the conduction band will relax and transfer to a state in the molecule, producing a long-lived charge-separated state that facilitates charge extraction and thereby enables photochemical reactions. Characterizing the dynamics of the charge-separation process and the electronic states involved is essential for a microscopic understanding of photocatalysis involving these materials, but this information is obscured in ensemble measurements due to the random placement of molecules on the nanorod surfaces. Here, we show that measurements on individual CdSe/CdS core/shell nanorods functionalized by single methyl viologen molecules provide information about the distribution of electron-transfer rates from confined states in the nanorods to states in the molecules. By comparing this transfer-rate distribution to the predictions of a tight-binding model, we find that charge transfer most likely involves hot electrons in an excited conduction-band state, rather than electrons that have fully thermalized to the conduction-band edge. The ability to extract hot electrons from semiconductor nanocrystals may help enable energy-efficient photocatalysis, and the single-particle charge-transfer method may serve as a widely applicable tool to probe the spatial distribution of electronic states in nanocrystals.