Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies

Abstract

Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play a necessary part in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free-energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We introduce a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This method incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectric continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganizationmore » energies in close agreement with experimental values for two experimentally studied PCET systems.« less

Authors:
 [1];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of Illinois at Urbana-Champaign, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388876
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 12; Journal Issue: 6; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ghosh, Soumya, Soudackov, Alexander V., and Hammes-Schiffer, Sharon. Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies. United States: N. p., 2016. Web. doi:10.1021/acs.jctc.6b00233.
Copy to clipboard
Ghosh, Soumya, Soudackov, Alexander V., & Hammes-Schiffer, Sharon. Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies. United States. https://doi.org/10.1021/acs.jctc.6b00233
Copy to clipboard
Ghosh, Soumya, Soudackov, Alexander V., and Hammes-Schiffer, Sharon. Mon . "Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies". United States. https://doi.org/10.1021/acs.jctc.6b00233. https://www.osti.gov/servlets/purl/1388876.
Copy to clipboard
@article{osti_1388876,
title = {Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies},
author = {Ghosh, Soumya and Soudackov, Alexander V. and Hammes-Schiffer, Sharon},
abstractNote = {Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play a necessary part in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free-energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We introduce a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This method incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectric continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems.},
doi = {10.1021/acs.jctc.6b00233},
journal = {Journal of Chemical Theory and Computation},
number = 6,
volume = 12,
place = {United States},
year = {Mon Apr 25 00:00:00 EDT 2016},
month = {Mon Apr 25 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jctc.6b00233
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Light-Induced Redox Reactions in Nanocrystalline Systems
journal, January 1995

  • Hagfeldt, Anders.; Graetzel, Michael.
  • Chemical Reviews, Vol. 95, Issue 1
  • DOI: 10.1021/cr00033a003

Towards optimisation of electron transfer processes in dye sensitised solar cells
journal, July 2004

  • Durrant, James R.; Haque, Saif A.; Palomares, Emilio
  • Coordination Chemistry Reviews, Vol. 248, Issue 13-14
  • DOI: 10.1016/j.ccr.2004.03.014

Electrochemistry and bioelectrochemistry towards the single-molecule level: Theoretical notions and systems
journal, May 2005

Molecular Approaches to Solar Energy Conversion with Coordination Compounds Anchored to Semiconductor Surfaces
journal, October 2005

The role of electron transfer in photocatalysis: Fact and fictions
journal, November 2012

Theoretical Insights into Photoinduced Charge Transfer and Catalysis at Oxide Interfaces
journal, December 2012

  • Akimov, Alexey V.; Neukirch, Amanda J.; Prezhdo, Oleg V.
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr3004899

Proton-Coupled Electron Transfer: Moving Together and Charging Forward
journal, July 2015

  • Hammes-Schiffer, Sharon
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04087

On the Theory of Electrochemical and Chemical Electron Transfer Processes
journal, January 1959

  • Marcus, R. A.
  • Canadian Journal of Chemistry, Vol. 37, Issue 1
  • DOI: 10.1139/v59-022

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964

On the Theory of Electron‐Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions
journal, July 1965

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 43, Issue 2
  • DOI: 10.1063/1.1696792

Outer-sphere electron transfer reactions at an electrode
journal, February 1987

Electronic friction and electron transfer rates at metallic electrodes
journal, November 1993

  • Smith, Barton B.; Hynes, James T.
  • The Journal of Chemical Physics, Vol. 99, Issue 9
  • DOI: 10.1063/1.465843

Fermi Golden Rule Approach to Evaluating Outer-Sphere Electron-Transfer Rate Constants at Semiconductor/Liquid Interfaces
journal, December 1997

  • Royea, William J.; Fajardo, Arnel M.; Lewis, Nathan S.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 51
  • DOI: 10.1021/jp972222y

Use of the dielectric sphere model for the calculation of the effect of a solvent on the kinetics of chemical reactions with charge transer. Communication 1. Energy of reorganization of a polar medium
journal, March 1985

  • German, �. D.; Kharkats, Yu. I.
  • Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 34, Issue 3
  • DOI: 10.1007/BF00947723

Reorganization free energy for electron transfers at liquid-liquid and dielectric semiconductor-liquid interfaces
journal, February 1990

The multi-configurational adiabatic electron transfer theory and its invariance under transformations of charge density basis functions
journal, February 1994

Solvent reorganization energy of electron-transfer reactions in polar solvents
journal, April 2004

  • Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 120, Issue 16
  • DOI: 10.1063/1.1676122

Reorganization energy of electron transfer processes in ionic fluids: A molecular Debye-Hückel approach
journal, March 2013

  • Xiao, Tiejun; Song, Xueyu
  • The Journal of Chemical Physics, Vol. 138, Issue 11
  • DOI: 10.1063/1.4794790

Solvent Reorganization and Donor/Acceptor Coupling in Electron-Transfer Processes: Self-Consistent Reaction Field Theory and ab Initio Applications
journal, August 1995

  • Liu, Yi-Ping; Newton, Marshall D.
  • The Journal of Physical Chemistry, Vol. 99, Issue 33
  • DOI: 10.1021/j100033a004

Electron Transfer in a Radical Ion Pair:  Quantum Calculations of the Solvent Reorganization Energy
journal, December 2006

  • Caricato, Marco; Ingrosso, Francesca; Mennucci, Benedetta
  • The Journal of Physical Chemistry B, Vol. 110, Issue 49
  • DOI: 10.1021/jp0632586

Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model
journal, April 2014

  • Ghosh, Soumya; Horvath, Samantha; Soudackov, Alexander V.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 5
  • DOI: 10.1021/ct500051e

A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
journal, August 1997

  • Cancès, E.; Mennucci, B.; Tomasi, J.
  • The Journal of Chemical Physics, Vol. 107, Issue 8
  • DOI: 10.1063/1.474659

New applications of integral equations methods for solvation continuum models: ionic solutions and liquid crystals
journal, January 1998

  • Cancès, Eric; Mennucci, Benedetta
  • Journal of Mathematical Chemistry, Vol. 23, Issue 3/4, p. 309-326
  • DOI: 10.1023/A:1019133611148

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

The Reorganization Energy of Azurin in Bulk Solution and in the Electrochemical Scanning Tunneling Microscopy Setup
journal, March 2005

  • Corni, Stefano
  • The Journal of Physical Chemistry B, Vol. 109, Issue 8
  • DOI: 10.1021/jp0459920

Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes
journal, December 2014

  • Ghosh, Soumya; Hammes-Schiffer, Sharon
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz5023784

A new and rigorous method for calculating intramolecular reorganization energies for electron-transfer reactions: applied for self-exchange reactions involving alkyl and benzyl radicals
journal, October 1991

  • Mikkelsen, Kurt V.; Pedersen, Steen U.; Lund, Henning
  • The Journal of Physical Chemistry, Vol. 95, Issue 22
  • DOI: 10.1021/j100175a087

Calculations of Intramolecular Reorganization Energies for Electron-Transfer Reactions Involving Organic Systems
journal, January 1996

  • Jakobsen, Steen; Mikkelsen, Kurt V.; Pedersen, Steen U.
  • The Journal of Physical Chemistry, Vol. 100, Issue 18
  • DOI: 10.1021/jp9535250

Reorganization energies in benzene, naphthalene, and anthracene
journal, November 1994

Diffuse layer effects due to adsorbed ions and inner layer polarizability
journal, November 1972

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

Advances in electronic structure theory
book, January 2005

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

On the parameterization of the local correlation functional. What is Becke-3-LYP?
journal, April 1997

Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules
journal, January 1971

  • Ditchfield, R.; Hehre, W. J.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 54, Issue 2
  • DOI: 10.1063/1.1674902

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

A new definition of cavities for the computation of solvation free energies by the polarizable continuum model
journal, August 1997

  • Barone, Vincenzo; Cossi, Maurizio; Tomasi, Jacopo
  • The Journal of Chemical Physics, Vol. 107, Issue 8
  • DOI: 10.1063/1.474671

Continuous and smooth potential energy surface for conductorlike screening solvation model using fixed points with variable areas
journal, February 2009

  • Su, Peifeng; Li, Hui
  • The Journal of Chemical Physics, Vol. 130, Issue 7
  • DOI: 10.1063/1.3077917

Evaluation of solvated radii of ions in non-aqueous solvents
journal, June 1979

Theoretical Analysis of the Sequential Proton-Coupled Electron Transfer Mechanisms for H 2 Oxidation and Production Pathways Catalyzed by Nickel Molecular Electrocatalysts
journal, January 2012

  • Fernandez, Laura E.; Horvath, Samantha; Hammes-Schiffer, Sharon
  • The Journal of Physical Chemistry C, Vol. 116, Issue 4
  • DOI: 10.1021/jp210690q

Adiabatic and Non-adiabatic Concerted Proton−Electron Transfers. Temperature Effects in the Oxidation of Intramolecularly Hydrogen-Bonded Phenols
journal, August 2007

  • Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
  • Journal of the American Chemical Society, Vol. 129, Issue 32
  • DOI: 10.1021/ja071150d

Concerted Proton−Electron Transfer: Effect of Hydroxylic Additives on the Reduction of Benzophenone, 4-Cyanobenzophenone, and 4,4′-Dicyanobenzophenone
journal, September 2009

  • Wang, Shihua; Singh, Pradyumna S.; Evans, Dennis H.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 38
  • DOI: 10.1021/jp904976v
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    2′-Deoxy-2′-fluoro-arabinonucleic acid: a valid alternative to DNA for biotechnological applications using charge transport
    journal, January 2019

    • Teo, Ruijie D.; Smithwick, Elizabeth R.; Migliore, Agostino
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 41
    • DOI: 10.1039/c9cp04805g

    Post-transition state bifurcations induce dynamical detours in Pummerer-like reactions
    journal, January 2018

    • Hare, Stephanie R.; Li, Ang; Tantillo, Dean J.
    • Chemical Science, Vol. 9, Issue 48
    • DOI: 10.1039/c8sc02653j
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: