Concerted proton-electron transfer reactions in the Marcus inverted region

Giovanny A. Parada, Zachary K. Goldsmith, Scott Kolmar, Belinda Pettersson Rimgard, Brandon Q. Mercado, Leif Hammarström, Sharon Hammes-Schiffer, James M. Mayer

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.

Original languageEnglish
Pages (from-to)471-475
Number of pages5
JournalScience (New York, N.Y.)
Volume364
Issue number6439
DOIs
Publication statusPublished - May 3 2019

Fingerprint

Protons
Electrons
Genetic Recombination
Phenol
Thermodynamics
pyridine
anthracene

ASJC Scopus subject areas

  • General

Cite this

Parada, G. A., Goldsmith, Z. K., Kolmar, S., Pettersson Rimgard, B., Mercado, B. Q., Hammarström, L., ... Mayer, J. M. (2019). Concerted proton-electron transfer reactions in the Marcus inverted region. Science (New York, N.Y.), 364(6439), 471-475. https://doi.org/10.1126/science.aaw4675

Concerted proton-electron transfer reactions in the Marcus inverted region. / Parada, Giovanny A.; Goldsmith, Zachary K.; Kolmar, Scott; Pettersson Rimgard, Belinda; Mercado, Brandon Q.; Hammarström, Leif; Hammes-Schiffer, Sharon; Mayer, James M.

In: Science (New York, N.Y.), Vol. 364, No. 6439, 03.05.2019, p. 471-475.

Research output: Contribution to journalArticle

Parada, GA, Goldsmith, ZK, Kolmar, S, Pettersson Rimgard, B, Mercado, BQ, Hammarström, L, Hammes-Schiffer, S & Mayer, JM 2019, 'Concerted proton-electron transfer reactions in the Marcus inverted region', Science (New York, N.Y.), vol. 364, no. 6439, pp. 471-475. https://doi.org/10.1126/science.aaw4675
Parada GA, Goldsmith ZK, Kolmar S, Pettersson Rimgard B, Mercado BQ, Hammarström L et al. Concerted proton-electron transfer reactions in the Marcus inverted region. Science (New York, N.Y.). 2019 May 3;364(6439):471-475. https://doi.org/10.1126/science.aaw4675
Parada, Giovanny A. ; Goldsmith, Zachary K. ; Kolmar, Scott ; Pettersson Rimgard, Belinda ; Mercado, Brandon Q. ; Hammarström, Leif ; Hammes-Schiffer, Sharon ; Mayer, James M. / Concerted proton-electron transfer reactions in the Marcus inverted region. In: Science (New York, N.Y.). 2019 ; Vol. 364, No. 6439. pp. 471-475.
@article{748024dcf5aa4b34a54349ad6538e09d,
title = "Concerted proton-electron transfer reactions in the Marcus inverted region",
abstract = "Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.",
author = "Parada, {Giovanny A.} and Goldsmith, {Zachary K.} and Scott Kolmar and {Pettersson Rimgard}, Belinda and Mercado, {Brandon Q.} and Leif Hammarstr{\"o}m and Sharon Hammes-Schiffer and Mayer, {James M.}",
year = "2019",
month = "5",
day = "3",
doi = "10.1126/science.aaw4675",
language = "English",
volume = "364",
pages = "471--475",
journal = "Science",
issn = "0036-8075",
publisher = "American Association for the Advancement of Science",
number = "6439",

}

TY - JOUR

T1 - Concerted proton-electron transfer reactions in the Marcus inverted region

AU - Parada, Giovanny A.

AU - Goldsmith, Zachary K.

AU - Kolmar, Scott

AU - Pettersson Rimgard, Belinda

AU - Mercado, Brandon Q.

AU - Hammarström, Leif

AU - Hammes-Schiffer, Sharon

AU - Mayer, James M.

PY - 2019/5/3

Y1 - 2019/5/3

N2 - Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.

AB - Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.

UR - http://www.scopus.com/inward/record.url?scp=85065554807&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85065554807&partnerID=8YFLogxK

U2 - 10.1126/science.aaw4675

DO - 10.1126/science.aaw4675

M3 - Article

VL - 364

SP - 471

EP - 475

JO - Science

JF - Science

SN - 0036-8075

IS - 6439

ER -