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Title: Voltage-induced long-range coherent electron transfer through organic molecules

Abstract

Biological structures rely on kinetically tuned charge transfer reactions for energy conversion, biocatalysis, and signaling as well as for oxidative damage repair. Unlike man-made electrical circuitry, which uses metals and semiconductors to direct current flow, charge transfer in living systems proceeds via biomolecules that are nominally insulating. Long-distance charge transport, which is observed routinely in nucleic acids, peptides, and proteins, is believed to arise from a sequence of thermally activated hopping steps. However, a growing number of experiments find limited temperature dependence for electron transfer over tens of nanometers. To account for these observations, we propose a temperature-independent mechanism based on the electric potential difference that builds up along the molecule as a precursor of electron transfer. Specifically, the voltage changes the nature of the electronic states away from being sharply localized so that efficient resonant tunneling across long distances becomes possible without thermal assistance. This mechanism is general and is expected to be operative in molecules where the electronic states densely fill a wide energy window (on the scale of electronvolts) above or below the gap between the highest-occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). We show that this effect can explain the temperature-independent chargemore » transport through DNA and the strongly voltage-dependent currents that are measured through organic semiconductors and peptides.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States); Univ. of Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Israel Science Foundation
OSTI Identifier:
1498587
Alternate Identifier(s):
OSTI ID: 1608631
Grant/Contract Number:  
SC0010662; FG02-07ER46430; 1889/16
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 13; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; electron transfer; organic molecules; electric field delocalization

Citation Formats

Michaeli, Karen, Beratan, David N., Waldeck, David H., and Naaman, Ron. Voltage-induced long-range coherent electron transfer through organic molecules. United States: N. p., 2019. Web. doi:10.1073/pnas.1816956116.
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Michaeli, Karen, Beratan, David N., Waldeck, David H., & Naaman, Ron. Voltage-induced long-range coherent electron transfer through organic molecules. United States. https://doi.org/10.1073/pnas.1816956116
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Michaeli, Karen, Beratan, David N., Waldeck, David H., and Naaman, Ron. Thu . "Voltage-induced long-range coherent electron transfer through organic molecules". United States. https://doi.org/10.1073/pnas.1816956116.
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@article{osti_1498587,
title = {Voltage-induced long-range coherent electron transfer through organic molecules},
author = {Michaeli, Karen and Beratan, David N. and Waldeck, David H. and Naaman, Ron},
abstractNote = {Biological structures rely on kinetically tuned charge transfer reactions for energy conversion, biocatalysis, and signaling as well as for oxidative damage repair. Unlike man-made electrical circuitry, which uses metals and semiconductors to direct current flow, charge transfer in living systems proceeds via biomolecules that are nominally insulating. Long-distance charge transport, which is observed routinely in nucleic acids, peptides, and proteins, is believed to arise from a sequence of thermally activated hopping steps. However, a growing number of experiments find limited temperature dependence for electron transfer over tens of nanometers. To account for these observations, we propose a temperature-independent mechanism based on the electric potential difference that builds up along the molecule as a precursor of electron transfer. Specifically, the voltage changes the nature of the electronic states away from being sharply localized so that efficient resonant tunneling across long distances becomes possible without thermal assistance. This mechanism is general and is expected to be operative in molecules where the electronic states densely fill a wide energy window (on the scale of electronvolts) above or below the gap between the highest-occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). We show that this effect can explain the temperature-independent charge transport through DNA and the strongly voltage-dependent currents that are measured through organic semiconductors and peptides.},
doi = {10.1073/pnas.1816956116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 13,
volume = 116,
place = {United States},
year = {Thu Mar 07 00:00:00 EST 2019},
month = {Thu Mar 07 00:00:00 EST 2019}
}
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https://doi.org/10.1073/pnas.1816956116
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