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Title: Electrode Reactions in Slowly Relaxing Media

Abstract

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamically freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden dropmore » with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. Arizona State Univ., Tempe, AZ (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1407474
Alternate Identifier(s):
OSTI ID: 1420660
Report Number(s):
BNL-114501-2017-JA
Journal ID: ISSN 0021-9606; R&D Project: CO037; KC0304030; TRN: US1703050
Grant/Contract Number:  
SC0012704; SC0015641
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Matyushov, Dmitry V., and Newton, Marshall D. Electrode Reactions in Slowly Relaxing Media. United States: N. p., 2017. Web. doi:10.1063/1.5003022.
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Matyushov, Dmitry V., & Newton, Marshall D. Electrode Reactions in Slowly Relaxing Media. United States. https://doi.org/10.1063/1.5003022
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Matyushov, Dmitry V., and Newton, Marshall D. Fri . "Electrode Reactions in Slowly Relaxing Media". United States. https://doi.org/10.1063/1.5003022. https://www.osti.gov/servlets/purl/1407474.
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@article{osti_1407474,
title = {Electrode Reactions in Slowly Relaxing Media},
author = {Matyushov, Dmitry V. and Newton, Marshall D.},
abstractNote = {Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamically freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.},
doi = {10.1063/1.5003022},
journal = {Journal of Chemical Physics},
number = 19,
volume = 147,
place = {United States},
year = {Fri Nov 17 00:00:00 EST 2017},
month = {Fri Nov 17 00:00:00 EST 2017}
}
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Works referenced in this record:

Wave vector dependent static dielectric properties of associated liquids: Methanol
journal, December 1990

  • Fonseca, Teresa; Ladanyi, Branka M.
  • The Journal of Chemical Physics, Vol. 93, Issue 11
  • DOI: 10.1063/1.459345

Outer-sphere electron transfer in polar solvents
journal, July 1980

Adiabatic Electron Transfer in a Room-Temperature Ionic Liquid: Reaction Dynamics and Kinetics
journal, October 2009

  • Shim, Youngseon; Kim, Hyung J.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 39
  • DOI: 10.1021/jp9065407

Solvent reorganization of electron transitions in viscous solvents
journal, April 2006

  • Ghorai, Pradip K.; Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 124, Issue 14
  • DOI: 10.1063/1.2185102

Temperature Dependence of Charge-Transfer Fluorescence from Extended and U-shaped Donor−Bridge−Acceptor Systems in Glass-Forming Solvents †
journal, March 2002

  • Goes, Marijn; de Groot, Mattijs; Koeberg, Mattijs
  • The Journal of Physical Chemistry A, Vol. 106, Issue 10
  • DOI: 10.1021/jp012507h

Electron Transfer in Frozen Media
journal, January 1996

  • Chen, Pingyun; Meyer, Thomas J.
  • Inorganic Chemistry, Vol. 35, Issue 19
  • DOI: 10.1021/ic9512845

On the evaluation and analysis of the Marcus–Hush–Chidsey integral
journal, May 2011

On the Mechanism of Solvation Dynamics in Imidazolium-Based Ionic Liquids
journal, July 2013

  • Terranova, Z. L.; Corcelli, S. A.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp406419y

Solvation dynamics in electron-transfer, isomerization, and nonlinear optical processes: a unified Liouville-space theory
journal, August 1988

  • Yan, Yi Jing; Sparpaglione, Massimo; Mukamel, Shaul
  • The Journal of Physical Chemistry, Vol. 92, Issue 17
  • DOI: 10.1021/j100328a010

Static longitudinal dielectric function of model molecular fluids
journal, February 1992

  • Raineri, Fernando O.; Resat, Haluk; Friedman, Harold L.
  • The Journal of Chemical Physics, Vol. 96, Issue 4
  • DOI: 10.1063/1.461952

Does Marcus theory apply to redox processes in ionic liquids? A simulation study
journal, August 2007

Solvation structure and the time‐resolved Stokes shift in non‐Debye solvents
journal, July 1990

  • Fried, Laurence E.; Mukamel, Shaul
  • The Journal of Chemical Physics, Vol. 93, Issue 2
  • DOI: 10.1063/1.459119

The potential-dependence and the upper limits of electrochemical rate constants
journal, November 1968

On the Electron Transfer Mechanism Between Cytochrome c and Metal Electrodes. Evidence for Dynamic Control at Short Distances †
journal, October 2006

  • Yue, Hongjun; Khoshtariya, D.; Waldeck, D. H.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 40
  • DOI: 10.1021/jp0620670

Electron transfer in retrospect and prospect 1: Adiabatic electrode processes
journal, July 1999

Trap Models and Slow Dynamics in Supercooled Liquids
journal, January 2003

Adiabatic outer sphere electron transfer through the metal-electrolyte interface
journal, October 1991

  • Gorodyskii, A. V.; Karasevskii, A. I.; Matyushov, D. V.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 315, Issue 1-2
  • DOI: 10.1016/0022-0728(91)80058-x

Dielectric and transport properties of a supercooled symmetrical molten salt
journal, September 1999

On the Structure and Dynamics of Ionic Liquids
journal, February 2004

  • Del Pópolo, Mario G.; Voth, Gregory A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 5
  • DOI: 10.1021/jp0364699

Molecular dynamics simulations of atomically flat and nanoporous electrodes with a molten salt electrolyte
journal, January 2010

  • Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D.
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 1
  • DOI: 10.1039/b917592j

Potential-step transient response of an electrochemical system
journal, March 1994

A phenomenological model of dynamical arrest of electron transfer in solvents in the glass-transition region
journal, February 2005

  • Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.1851981

Rapid Electron Tunneling Through Oligophenylenevinylene Bridges
journal, February 2001

Solvation Dynamics and Electric Field Relaxation in an Imidazolium-PF 6 Ionic Liquid:  from Room Temperature to the Glass Transition †
journal, May 2007

  • Ito, Naoki; Richert, Ranko
  • The Journal of Physical Chemistry B, Vol. 111, Issue 18
  • DOI: 10.1021/jp0640023

Ferrocene/Ferrocenium Redox Couple at Au(111)/Ionic Liquid and Au(111)/Acetonitrile Interfaces: A Molecular-Level View at the Elementary Act
journal, March 2014

  • Nikitina, Victoria A.; Kislenko, Sergey A.; Nazmutdinov, Renat R.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp4072108

On the evaluation of the Marcus–Hush–Chidsey integral
journal, April 2012

Velocity Correlation and Relative Diffusion in Simple Liquids
journal, December 1975

Standard electrode potential, Tafel equation, and the solvation thermodynamics
journal, June 2009

  • Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 130, Issue 23
  • DOI: 10.1063/1.3152847

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

Ultra-Broadband Dielectric and Optical Kerr-Effect Study of the Ionic Liquids Ethyl and Propylammonium Nitrate
journal, July 2014

  • Sonnleitner, Thomas; Turton, David A.; Hefter, Glenn
  • The Journal of Physical Chemistry B, Vol. 119, Issue 29
  • DOI: 10.1021/jp502935t

Temperature dependence of the electronic factor in the nonadiabatic electron transfer at metal and semiconductor electrodes
journal, March 2001

Simple theory of current fluctuations and noise in bridge-mediated nano-junctions
journal, August 2008

Solvent response and dielectric relaxation in supercooled butyronitrile
journal, July 2006

  • Ito, Naoki; Duvvuri, Kalyan; Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 125, Issue 2
  • DOI: 10.1063/1.2212420

Estimation of the rate constant for electron transfer in room temperature ionic liquids
journal, September 2011

Nonergodic activated kinetics in polar media
journal, April 2009

  • Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 130, Issue 16
  • DOI: 10.1063/1.3119639

New experimental evidence concerning the magnitude of the activation parameters for fast heterogeneous electron transfer reactions
journal, September 1991

  • Baranski, Andrzej S.; Winkler, Krzysztof; Fawcett, W. Ronald
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 313, Issue 1-2
  • DOI: 10.1016/0022-0728(91)85194-t

Heterogeneous dynamics in liquids: fluctuations in space and time
journal, May 2002

Can Marcus Theory Be Applied to Redox Processes in Ionic Liquids? A Comparative Simulation Study of Dimethylimidazolium Liquids and Acetonitrile
journal, September 2007

  • Lynden-Bell, R. M.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 36
  • DOI: 10.1021/jp074298s

Structure and dynamics of molten salts
journal, September 1986

Dynamical effects in electron transfer reactions
journal, May 1986

  • Sumi, H.; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 84, Issue 9
  • DOI: 10.1063/1.449978

Protein dynamics: from rattling in a cage to structural relaxation
journal, January 2015

Triplet state solvation dynamics: Basics and applications
journal, November 2000

  • Richert, Ranko
  • The Journal of Chemical Physics, Vol. 113, Issue 19
  • DOI: 10.1063/1.1319174

Understanding Ionic Liquids through Atomistic and Coarse-Grained Molecular Dynamics Simulations
journal, November 2007

  • Wang, Yanting; Jiang, Wei; Yan, Tianying
  • Accounts of Chemical Research, Vol. 40, Issue 11
  • DOI: 10.1021/ar700160p

Simulations of Solvation and Solvation Dynamics in an Idealized Ionic Liquid Model
journal, May 2012

  • Roy, Durba; Maroncelli, Mark
  • The Journal of Physical Chemistry B, Vol. 116, Issue 20
  • DOI: 10.1021/jp301359w

The stable states picture of chemical reactions. I. Formulation for rate constants and initial condition effects
journal, September 1980

  • Northrup, Scott H.; Hynes, James T.
  • The Journal of Chemical Physics, Vol. 73, Issue 6
  • DOI: 10.1063/1.440484

Reorganization Energy of Electron Transfer in Viscous Solvents above the Glass Transition
journal, February 2006

  • Ghorai, Pradip K.; Matyushov, Dmitry V.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 4
  • DOI: 10.1021/jp055235h

Electrochemical charge transfer at a metallic electrode: A simulation study
journal, March 2008

  • Reed, Stewart K.; Madden, Paul A.; Papadopoulos, Aristides
  • The Journal of Chemical Physics, Vol. 128, Issue 12
  • DOI: 10.1063/1.2844801

A molecular theory of electron transfer reactions in polar liquids
journal, July 1993

Homogeneous and heterogeneous optical and thermal electron transfer
journal, May 1968

Glassy Protein Dynamics and Gigantic Solvent Reorganization Energy of Plastocyanin
journal, April 2008

  • LeBard, David N.; Matyushov, Dmitry V.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 16
  • DOI: 10.1021/jp709586e

Energetics and Kinetics of Primary Charge Separation in Bacterial Photosynthesis
journal, August 2008

  • LeBard, David N.; Kapko, Vitaliy; Matyushov, Dmitry V.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 33
  • DOI: 10.1021/jp8016503

Are the current theories of electron transfer applicable to reactions in ionic liquids? An ESR-study on the TCNE/TCNE − ˙ couple
journal, January 2016

  • Mladenova, B. Y.; Kattnig, D. R.; Sudy, B.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 21
  • DOI: 10.1039/c6cp01750a

Temperature Dependence of the Dielectric Properties and Dynamics of Ionic Liquids
journal, March 2009

  • Hunger, Johannes; Stoppa, Alexander; Schrödle, Simon
  • ChemPhysChem, Vol. 10, Issue 4
  • DOI: 10.1002/cphc.200800483

Energetics of charge transfer reactions in solvents of dipolar and higher order multipolar character. I. Theory
journal, May 1996

  • Perng, Baw‐Ching; Newton, Marshall D.; Raineri, Fernando O.
  • The Journal of Chemical Physics, Vol. 104, Issue 18
  • DOI: 10.1063/1.471431

Energetics of Electron-Transfer Reactions in Soft Condensed Media
journal, April 2007

  • Matyushov, Dmitry V.
  • Accounts of Chemical Research, Vol. 40, Issue 4
  • DOI: 10.1021/ar7000167

Ionic Liquids at Electrified Interfaces
journal, March 2014

  • Fedorov, Maxim V.; Kornyshev, Alexei A.
  • Chemical Reviews, Vol. 114, Issue 5
  • DOI: 10.1021/cr400374x

Protein electron transfer: Dynamics and statistics
journal, July 2013

  • Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 139, Issue 2
  • DOI: 10.1063/1.4812788

Multiple Mechanisms for Electron Transfer at Metal/Self-Assembled Monolayer/Room-Temperature Ionic Liquid Junctions: Dynamical Arrest versus Frictional Control and Non-Adiabaticity
journal, May 2009

  • Khoshtariya, Dimitri E.; Dolidze, Tina D.; van Eldik, Rudi
  • Chemistry - A European Journal, Vol. 15, Issue 21
  • DOI: 10.1002/chem.200802450

Kinetic Parameters for Cytochrome c via Insulated Electrode Voltammetry
journal, January 1996

  • Terrettaz, Samuel; Cheng, Jun; Miller, Cary J.
  • Journal of the American Chemical Society, Vol. 118, Issue 33
  • DOI: 10.1021/ja960866y

Dipole Solvation in Nondipolar Solvents:  Experimental Studies of Reorganization Energies and Solvation Dynamics †
journal, January 1996

  • Reynolds, L.; Gardecki, J. A.; Frankland, S. J. V.
  • The Journal of Physical Chemistry, Vol. 100, Issue 24
  • DOI: 10.1021/jp953110e

Electrochemical electron transfer: a diffusion-reaction equation approach
journal, June 1992

Dynamics and structure of room temperature ionic liquids
journal, November 2014

Protein electron transfer: is biology (thermo)dynamic?
journal, November 2015

Time-dependent fluorescence solvent shifts, dielectric friction, and nonequilibrium solvation in polar solvents
journal, September 1985

  • Van der Zwan, G.; Hynes, James T.
  • The Journal of Physical Chemistry, Vol. 89, Issue 20
  • DOI: 10.1021/j100266a008

Measurements of the Complete Solvation Response in Ionic Liquids †
journal, May 2007

  • Arzhantsev, Sergei; Jin, Hui; Baker, Gary A.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 18
  • DOI: 10.1021/jp067273m

Femtosecond solvation dynamics of water
journal, June 1994

  • Jimenez, Ralph; Fleming, Graham R.; Kumar, P. V.
  • Nature, Vol. 369, Issue 6480
  • DOI: 10.1038/369471a0

Nonadiabatic Electron Transfer at Metal Surfaces
journal, March 2000

  • Gosavi, Shachi; Marcus, R. A.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 9
  • DOI: 10.1021/jp9933673

Long Distance Electron Transfer at the Metal/Alkanethiol/Ionic Liquid Interface
journal, July 2014

  • Nikitina, Victoria A.; Rudnev, Alexander V.; Tsirlina, Galina A.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp5055843

Interactions and Dynamics in Ionic Liquids
journal, April 2008

  • Stoppa, Alexander; Hunger, Johannes; Buchner, Richard
  • The Journal of Physical Chemistry B, Vol. 112, Issue 16
  • DOI: 10.1021/jp800852z

Temperature dependence of the electrical conductivity of imidazolium ionic liquids
journal, February 2008

  • Leys, Jan; Wübbenhorst, Michael; Preethy Menon, Chirukandath
  • The Journal of Chemical Physics, Vol. 128, Issue 6
  • DOI: 10.1063/1.2827462

Supercooled Liquids and Glasses
journal, January 1996

  • Ediger, M. D.; Angell, C. A.; Nagel, Sidney R.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953538d

Double Layer in Ionic Liquids: Overscreening versus Crowding
journal, January 2011

Are mean-field spin-glass models relevant for the structural glass transition?
journal, May 2000

Effect of the Metal on Electron Transfer across Self-Assembled Monolayers
journal, April 2001

  • Finklea, H. O.; Yoon, K.; Chamberlain, E.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 15
  • DOI: 10.1021/jp0041510

Observation of the Global Dynamic Collectivity of a Hydration Shell around Apomyoglobin
journal, February 2017

  • Qin, Yangzhong; Zhang, Luyuan; Wang, Lijuan
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 6
  • DOI: 10.1021/acs.jpclett.7b00205

Electrostatic ion—solvent interaction
journal, January 1991

Molecular Layering of Fluorinated Ionic Liquids at a Charged Sapphire (0001) Surface
journal, October 2008

Entropy of Attractive Forces and Molecular Nonsphericity in Real Liquids: A Measure of Structural Ordering
journal, February 1995

  • Schmid, Roland; Matyushov, Dmitry V.
  • The Journal of Physical Chemistry, Vol. 99, Issue 8
  • DOI: 10.1021/j100008a023

Solvation dynamics for an ion pair in a polar solvent: Time‐dependent fluorescence and photochemical charge transfer
journal, May 1991

  • Carter, Emily A.; Hynes, James T.
  • The Journal of Chemical Physics, Vol. 94, Issue 9
  • DOI: 10.1063/1.460431

Three Classes of Motion in the Dynamic Neutron-Scattering Susceptibility of a Globular Protein
journal, September 2011

Protein dynamics in a broad frequency range: Dielectric spectroscopy studies
journal, January 2015

Solvent relaxation of oxazine-4 in 2-methyltetrahydrofuran
journal, May 1995

Broken ergodicity
journal, December 1982

Well and barrier dynamics and electron transfer rates. A molecular dynamics study
journal, October 1993

Adiabaticity of electron transfer at an electrode
journal, February 1987

  • Morgan, John D.; Wolynes, Peter G.
  • The Journal of Physical Chemistry, Vol. 91, Issue 4
  • DOI: 10.1021/j100288a023

Electrode polarization and charge transport at solid interfaces
journal, November 2009

The static dielectric permittivity of ionic liquids
journal, April 2014

On Spectral Relaxation in Proteins†¶‖
journal, January 2000

Dipolar Solvation Dynamics in Room Temperature Ionic Liquids: An Effective Medium Calculation Using Dielectric Relaxation Data
journal, October 2008

  • Kashyap, Hemant K.; Biswas, Ranjit
  • The Journal of Physical Chemistry B, Vol. 112, Issue 39
  • DOI: 10.1021/jp8044516

Solvation Dynamics of Dipolar Probes in Dipolar Room Temperature Ionic Liquids: Separation of Ion−Dipole and Dipole−Dipole Interaction Contributions
journal, January 2010

  • Kashyap, Hemant K.; Biswas, Ranjit
  • The Journal of Physical Chemistry B, Vol. 114, Issue 1
  • DOI: 10.1021/jp906023p

Dynamic solvent effects on outer‐sphere electron transfer
journal, August 1987

  • Rips, Ilya; Jortner, Joshua
  • The Journal of Chemical Physics, Vol. 87, Issue 4
  • DOI: 10.1063/1.453184

Free energy functionals for polarization fluctuations: Pekar factor revisited
journal, February 2017

  • Dinpajooh, Mohammadhasan; Newton, Marshall D.; Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 146, Issue 6
  • DOI: 10.1063/1.4975625

A theory of adiabatic electron-transfer reactions
journal, June 1986

  • Schmickler, Wolfgang
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 204, Issue 1-2
  • DOI: 10.1016/0022-0728(86)80505-8

Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc 1 complex
journal, April 2015

  • Martin, Daniel R.; Matyushov, Dmitry V.
  • The Journal of Chemical Physics, Vol. 142, Issue 16
  • DOI: 10.1063/1.4919222

Nonlocal electrostatic effects on electron-transfer activation energies: some consequences for and comparisons with electrochemical and homogeneous-phase kinetics
journal, February 1990

  • Phelps, Donald K.; Kornyshev, A. A.; Weaver, Michael J.
  • The Journal of Physical Chemistry, Vol. 94, Issue 4
  • DOI: 10.1021/j100367a048

Reorganization Energy for Electron Transfer at Film-Modified Electrode Surfaces: A Dielectric Continuum Model
journal, July 1994

  • Liu, Yi-Ping; Newton, Marshall D.
  • The Journal of Physical Chemistry, Vol. 98, Issue 29
  • DOI: 10.1021/j100080a011

Electrochemical Rate Constants in Room Temperature Ionic Liquids: The Oxidation of a Series of Ferrocene Derivatives
journal, May 2006

  • Fietkau, Nicole; Clegg, Antony D.; Evans, Russell G.
  • ChemPhysChem, Vol. 7, Issue 5
  • DOI: 10.1002/cphc.200500709

Estimation of effective diameters for molecular fluids
journal, February 1990

  • Ben-Amotz, Dor.; Herschbach, Dudley R.
  • The Journal of Physical Chemistry, Vol. 94, Issue 3
  • DOI: 10.1021/j100366a003

Interfacial bridge-mediated electron transfer: mechanistic analysis based on electrochemical kinetics and theoretical modelling
journal, January 2007

  • Newton, Marshall D.; Smalley, John F.
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 5
  • DOI: 10.1039/b611448b

S PATIALLY H ETEROGENEOUS D YNAMICS IN S UPERCOOLED L IQUIDS
journal, October 2000

Über die Polarisation bei kathodischer Wasserstoffentwicklung
journal, January 1905

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