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Title: Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization

Abstract

Rate constants for bimolecular electron transfer (ET) increased with driving force, -ΔG°, reached a plateau, and then decreased in an inverted region. This rate data was described well by electron transfer theory subject to a diffusion-controlled limit. These were for ET from radical anions of polydecylthiophene (P3DT) to a series of acceptors in THF solution. When the donor was the smaller anion of quaterthiophene (T4•-) the inverted region was much less prominent, and still less so for when the donor was the anion of bithiophene (T2•-). Description of the data using ET theory identifies smaller electronic couplings for the highly-delocalized P3DT anions as enabling the inverted behavior: The presence of a Marcus inverted region is a consequence of delocalized electronic states. The results of this study further imply that electronic couplings smaller than usually found for molecules in contact could boost efficiency of energy storage by electron transfer, and identifies size-mismatch as an important concept in control of electronic couplings.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1670665
Report Number(s):
BNL-219915-2020-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704; AC02-98-CH10886
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 42; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; Electron transfer; Inverted region

Citation Formats

Takeda, Norihiko, and Miller, John R. Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization. United States: N. p., 2020. Web. doi:10.1021/jacs.0c04780.
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Takeda, Norihiko, & Miller, John R. Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization. United States. https://doi.org/10.1021/jacs.0c04780
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Takeda, Norihiko, and Miller, John R. Tue . "Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization". United States. https://doi.org/10.1021/jacs.0c04780. https://www.osti.gov/servlets/purl/1670665.
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@article{osti_1670665,
title = {Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization},
author = {Takeda, Norihiko and Miller, John R.},
abstractNote = {Rate constants for bimolecular electron transfer (ET) increased with driving force, -ΔG°, reached a plateau, and then decreased in an inverted region. This rate data was described well by electron transfer theory subject to a diffusion-controlled limit. These were for ET from radical anions of polydecylthiophene (P3DT) to a series of acceptors in THF solution. When the donor was the smaller anion of quaterthiophene (T4•-) the inverted region was much less prominent, and still less so for when the donor was the anion of bithiophene (T2•-). Description of the data using ET theory identifies smaller electronic couplings for the highly-delocalized P3DT anions as enabling the inverted behavior: The presence of a Marcus inverted region is a consequence of delocalized electronic states. The results of this study further imply that electronic couplings smaller than usually found for molecules in contact could boost efficiency of energy storage by electron transfer, and identifies size-mismatch as an important concept in control of electronic couplings.},
doi = {10.1021/jacs.0c04780},
journal = {Journal of the American Chemical Society},
number = 42,
volume = 142,
place = {United States},
year = {Tue Oct 13 00:00:00 EDT 2020},
month = {Tue Oct 13 00:00:00 EDT 2020}
}
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