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Title: Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer

Abstract

Electron-transfer theories predict that an increase in the quantum-mechanical mixing (H DA ) of electron donor and acceptor wavefunctions at the instant of electron transfer drives equilibrium constants toward unity. Kinetic and equilibrium studies of four acceptor–bridge–donor (A-B-D) compounds reported herein provide experimental validation of this prediction. The compounds have two redox-active groups that differ only by the orientation of the aromatic bridge: a phenyl–thiophene bridge (p) that supports strong electronic coupling of H DA > 1,000 cm −1 ; and a xylyl–thiophene bridge (x) that prevents planarization and decreases H DA < 100 cm −1 without a significant change in distance. Pulsed-light excitation allowed kinetic determination of the equilibrium constant, K eq . In agreement with theory, K eq (p) were closer to unity compared to K eq (x). A van’t Hoff analysis provided clear evidence of an adiabatic electron-transfer pathway for p-series and a nonadiabatic pathway for x-series. Collectively, the data show that the absolute magnitude of the thermodynamic driving force for electron transfers are decreased when adiabatic pathways are operative, a finding that should be taken into account in the design of hybrid materials for solar energy conversion.

Authors:
ORCiD logo; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1457096
Alternate Identifier(s):
OSTI ID: 1540281
Grant/Contract Number:  
SC0013461
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: 115 Journal Issue: 28; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology; Other Topics; electron transfer; electronic coupling; Gibbs free energy; equilibrium; solar energy

Citation Formats

Sampaio, Renato N., Piechota, Eric J., Troian-Gautier, Ludovic, Maurer, Andrew B., Hu, Ke, Schauer, Phil A., Blair, Amber D., Berlinguette, Curtis P., and Meyer, Gerald J. Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer. United States: N. p., 2018. Web. doi:10.1073/pnas.1722401115.
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Sampaio, Renato N., Piechota, Eric J., Troian-Gautier, Ludovic, Maurer, Andrew B., Hu, Ke, Schauer, Phil A., Blair, Amber D., Berlinguette, Curtis P., & Meyer, Gerald J. Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer. United States. doi:10.1073/pnas.1722401115.
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Sampaio, Renato N., Piechota, Eric J., Troian-Gautier, Ludovic, Maurer, Andrew B., Hu, Ke, Schauer, Phil A., Blair, Amber D., Berlinguette, Curtis P., and Meyer, Gerald J. Mon . "Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer". United States. doi:10.1073/pnas.1722401115.
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@article{osti_1457096,
title = {Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer},
author = {Sampaio, Renato N. and Piechota, Eric J. and Troian-Gautier, Ludovic and Maurer, Andrew B. and Hu, Ke and Schauer, Phil A. and Blair, Amber D. and Berlinguette, Curtis P. and Meyer, Gerald J.},
abstractNote = {Electron-transfer theories predict that an increase in the quantum-mechanical mixing (H DA ) of electron donor and acceptor wavefunctions at the instant of electron transfer drives equilibrium constants toward unity. Kinetic and equilibrium studies of four acceptor–bridge–donor (A-B-D) compounds reported herein provide experimental validation of this prediction. The compounds have two redox-active groups that differ only by the orientation of the aromatic bridge: a phenyl–thiophene bridge (p) that supports strong electronic coupling of H DA > 1,000 cm −1 ; and a xylyl–thiophene bridge (x) that prevents planarization and decreases H DA < 100 cm −1 without a significant change in distance. Pulsed-light excitation allowed kinetic determination of the equilibrium constant, K eq . In agreement with theory, K eq (p) were closer to unity compared to K eq (x). A van’t Hoff analysis provided clear evidence of an adiabatic electron-transfer pathway for p-series and a nonadiabatic pathway for x-series. Collectively, the data show that the absolute magnitude of the thermodynamic driving force for electron transfers are decreased when adiabatic pathways are operative, a finding that should be taken into account in the design of hybrid materials for solar energy conversion.},
doi = {10.1073/pnas.1722401115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 28,
volume = 115,
place = {United States},
year = {2018},
month = {6}
}
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DOI: 10.1073/pnas.1722401115
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