Q-model of electrode reactions: altering force constants of intramolecular vibrations

Matyushov, Dmitry V.; Newton, Marshall D.

doi:10.1039/c8cp03759k

Q-model of electrode reactions: altering force constants of intramolecular vibrations

Journal Article · Fri Aug 31 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp03759k· OSTI ID:1480972

^[1]; Newton, Marshall D. ^[2]

Arizona State Univ., Tempe, AZ (United States). Dept. of Physics and School of Molecular Sciences
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry

A theory of redox reactions involving electron transfer between a metal electrode and a molecule in solution is formulated in terms of two types of nuclear coordinates of the thermal bath: electrostatic polarization of the medium and local low-frequency vibrations. The polarization fluctuations follow Gaussian statistics. In contrast, the vibrational coordinate is allowed to change its force constant between two oxidation states of the reactant, which is projected onto non-Gaussian fluctuations of the reactant's electronic states. A closed-form analytical theory for the electrode redox reactions is formulated in terms of three reorganization energies: the reorganization energy for the electrostatic polarization of the medium and two internal (vibrational) reorganization energies for the reduced and oxidized states of the reactant. In conclusion, the theory predicts asymmetry between the cathodic and anodic branches of the electrode current driven by the corresponding difference in the vibrational force constants.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0015641

OSTI ID:: 1480972

Alternate ID(s):: OSTI ID: 1470573

Report Number(s):: BNL--209340-2018-JAAM

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 37 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Interfacial Electrochemistry Schmickler, Wolfgang; Santos, Elizabeth Springer Berlin, Heidelberg https://doi.org/10.1007/978-3-642-04937-8	book	January 2010
Homogeneous and heterogeneous optical and thermal electron transfer Hush, N. S. Electrochimica Acta, Vol. 13, Issue 5 https://doi.org/10.1016/0013-4686(68)80032-5	journal	May 1968
Outer-sphere electron transfer in polar solvents Zusman, L. D. Chemical Physics, Vol. 49, Issue 2 https://doi.org/10.1016/0301-0104(80)85267-0	journal	July 1980
Electron transfers in chemistry and biology Marcus, R. A.; Sutin, Norman Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3 https://doi.org/10.1016/0304-4173(85)90014-X	journal	August 1985
The potential-dependence and the upper limits of electrochemical rate constants Hale, J. M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 19, Issue 3 https://doi.org/10.1016/S0022-0728(68)80131-7	journal	November 1968
Asymmetry of inner-sphere reorganization energy for heterogeneous electron transfer Tsirlina, G. A.; Kharkats, Yu. I.; Nazmutdinov, R. R. Journal of Electroanalytical Chemistry, Vol. 450, Issue 1 https://doi.org/10.1016/S0022-0728(97)00618-9	journal	June 1998
Electron transfer in retrospect and prospect 1: Adiabatic electrode processes Hush, N. S. Journal of Electroanalytical Chemistry, Vol. 470, Issue 2 https://doi.org/10.1016/S0022-0728(99)00168-0	journal	July 1999
Non-Gaussian statistics of binding/unbinding events and the energetics of electron transfer reactions Matyushov, Dmitry V. Chemical Physics, Vol. 351, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.03.028	journal	July 2008
An experimental comparison of the Marcus–Hush and Butler–Volmer descriptions of electrode kinetics applied to cyclic voltammetry. The one electron reductions of europium (III) and 2-methyl-2-nitropropane studied at a mercury microhemisphere electrode Henstridge, Martin C.; Wang, Yijun; Limon-Petersen, Juan G. Chemical Physics Letters, Vol. 517, Issue 1-3 https://doi.org/10.1016/j.cplett.2011.10.004	journal	November 2011
Life of the Tafel equation: Current understanding and prospects for the second century Petrii, Oleg A.; Nazmutdinov, Renat R.; Bronshtein, Michael D. Electrochimica Acta, Vol. 52, Issue 11 https://doi.org/10.1016/j.electacta.2006.10.014	journal	March 2007
On the evaluation and analysis of the Marcus–Hush–Chidsey integral Oldham, Keith B.; Myland, Jan C. Journal of Electroanalytical Chemistry, Vol. 655, Issue 1 https://doi.org/10.1016/j.jelechem.2011.01.044	journal	May 2011
Asymmetric Marcus theory: Application to electrode kinetics Laborda, Eduardo; Henstridge, Martin C.; Compton, Richard G. Journal of Electroanalytical Chemistry, Vol. 667 https://doi.org/10.1016/j.jelechem.2011.12.011	journal	February 2012
On the evaluation of the Marcus–Hush–Chidsey integral Migliore, Agostino; Nitzan, Abraham Journal of Electroanalytical Chemistry, Vol. 671 https://doi.org/10.1016/j.jelechem.2012.02.026	journal	April 2012
Simple formula for asymmetric Marcus–Hush kinetics Zeng, Yi; Bai, Peng; Smith, Raymond B. Journal of Electroanalytical Chemistry, Vol. 748 https://doi.org/10.1016/j.jelechem.2015.04.018	journal	July 2015
Application of Asymmetric Marcus–Hush Theory to Voltammetry in Room-Temperature Ionic Liquids Tanner, Eden E. L.; Barnes, Edward O.; Tickell, Caitlin B. The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpcc.5b01174	journal	March 2015
Elucidating the Oxygen Reduction Reaction Kinetics and the Origins of the Anomalous Tafel Behavior at the Lithium–Oxygen Cell Cathode Sankarasubramanian, Shrihari; Seo, Jeongwook; Mizuno, Fuminori The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b09747	journal	February 2017
Second-order nonlinearity in poled-polymer systems Burland, Donald M.; Miller, Robert D.; Walsh, Cecilia A. Chemical Reviews, Vol. 94, Issue 1 https://doi.org/10.1021/cr00025a002	journal	January 1994
Dynamics of reactions in polar solvents. Semiclassical trajectory studies of electron-transfer and proton-transfer reactions Warshel, Arieh The Journal of Physical Chemistry, Vol. 86, Issue 12 https://doi.org/10.1021/j100209a016	journal	June 1982
Relation between the electron-transfer rate and the free energy change of reaction Tachiya, Masanori The Journal of Physical Chemistry, Vol. 93, Issue 20 https://doi.org/10.1021/j100357a005	journal	October 1989
The driving-force dependence of electrochemical rate parameters: origins of anodic-cathodic asymmetries for metal-aquo redox couples Hupp, Joseph T.; Weaver, Michael J. The Journal of Physical Chemistry, Vol. 88, Issue 25 https://doi.org/10.1021/j150669a015	journal	December 1984
Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates Miller, J. R.; Calcaterra, L. T.; Closs, G. L. Journal of the American Chemical Society, Vol. 106, Issue 10 https://doi.org/10.1021/ja00322a058	journal	May 1984
Large Electron Transfer Rate Effects from the Duschinsky Mixing of Vibrations Sando, Gerald M.; Spears, Kenneth G.; Hupp, Joseph T. The Journal of Physical Chemistry A, Vol. 105, Issue 22 https://doi.org/10.1021/jp004229c	journal	June 2001
Proton-Coupled Electron Transfer of an Osmium Aquo Complex on a Self-Assembled Monolayer on Gold Haddox, Robert M.; Finklea, Harry O. The Journal of Physical Chemistry B, Vol. 108, Issue 5 https://doi.org/10.1021/jp035967e	journal	February 2004
Electrostatic Potentials and Free Energies of Solvation of Polar and Charged Molecules Hummer, Gerhard; Pratt, Lawrence R.; García, Angel E. The Journal of Physical Chemistry B, Vol. 101, Issue 16 https://doi.org/10.1021/jp964037a	journal	April 1997
Classical and Quantum Simulation of Electron Transfer Through a Polypeptide Ungar, Lowell W.; Newton, Marshall D.; Voth, Gregory A. The Journal of Physical Chemistry B, Vol. 103, Issue 34 https://doi.org/10.1021/jp991057e	journal	August 1999
Nonadiabatic Electron Transfer at Metal Surfaces Gosavi, Shachi; Marcus, R. A. The Journal of Physical Chemistry B, Vol. 104, Issue 9 https://doi.org/10.1021/jp9933673	journal	March 2000
Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong Nature Chemistry, Vol. 9, Issue 5 https://doi.org/10.1038/nchem.2695	journal	January 2017
Charge transfer kinetics at the solid–solid interface in porous electrodes Bai, Peng; Bazant, Martin Z. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4585	journal	April 2014
Interfacial bridge-mediated electron transfer: mechanistic analysis based on electrochemical kinetics and theoretical modelling Newton, Marshall D.; Smalley, John F. Phys. Chem. Chem. Phys., Vol. 9, Issue 5 https://doi.org/10.1039/B611448B	journal	January 2007
A density functional theory based study of the electron transfer reaction at the cathode–electrolyte interface in lithium–air batteries Kazemiabnavi, Saeed; Dutta, Prashanta; Banerjee, Soumik Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C4CP06121G	journal	January 2015
Simple schemes in chemical electron transfer formalism beyond single-mode quadratic forms: environmental vibrational dispersion and anharmonic nuclear motion Kuznetsov, Aleksandr M.; Ulstrup, Jens Physical Chemistry Chemical Physics, Vol. 1, Issue 24 https://doi.org/10.1039/a906013h	journal	January 1999
Asymmetric Marcus–Hush theory for voltammetry Laborda, Eduardo; Henstridge, Martin C.; Batchelor-McAuley, Christopher Chemical Society Reviews, Vol. 42, Issue 12 https://doi.org/10.1039/c3cs35487c	journal	January 2013
Modeling the free energy surfaces of electron transfer in condensed phases Matyushov, Dmitry V.; Voth, Gregory A. The Journal of Chemical Physics, Vol. 113, Issue 13 https://doi.org/10.1063/1.1289886	journal	January 2000
Solvent reorganization energy of electron-transfer reactions in polar solvents Matyushov, Dmitry V. The Journal of Chemical Physics, Vol. 120, Issue 16 https://doi.org/10.1063/1.1676122	journal	April 2004
On the Theory of Electron‐Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions Marcus, R. A. The Journal of Chemical Physics, Vol. 43, Issue 2 https://doi.org/10.1063/1.1696792	journal	July 1965
The Franck‐Condon Principle and Its Application to Crystals Lax, Melvin The Journal of Chemical Physics, Vol. 20, Issue 11 https://doi.org/10.1063/1.1700283	journal	November 1952
Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I Marcus, R. A. The Journal of Chemical Physics, Vol. 24, Issue 5 https://doi.org/10.1063/1.1742724	journal	May 1956
Standard electrode potential, Tafel equation, and the solvation thermodynamics Matyushov, Dmitry V. The Journal of Chemical Physics, Vol. 130, Issue 23 https://doi.org/10.1063/1.3152847	journal	June 2009
Molecular model for aqueous ferrous–ferric electron transfer Kuharski, Robert A.; Bader, Joel S.; Chandler, David The Journal of Chemical Physics, Vol. 89, Issue 5 https://doi.org/10.1063/1.454929	journal	September 1988
Microscopic formulation of Marcus’ theory of electron transfer Zhou, Huan‐Xiang; Szabo, Attila The Journal of Chemical Physics, Vol. 103, Issue 9 https://doi.org/10.1063/1.470232	journal	September 1995
Free energy functionals for polarization fluctuations: Pekar factor revisited Dinpajooh, Mohammadhasan; Newton, Marshall D.; Matyushov, Dmitry V. The Journal of Chemical Physics, Vol. 146, Issue 6 https://doi.org/10.1063/1.4975625	journal	February 2017
Electrode redox reactions with polarizable molecules Matyushov, Dmitry V. The Journal of Chemical Physics, Vol. 148, Issue 15 https://doi.org/10.1063/1.5022709	journal	April 2018
Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface Chidsey, C. E. D. Science, Vol. 251, Issue 4996 https://doi.org/10.1126/science.251.4996.919	journal	February 1991
Application of the Method of Generating Function to Radiative and Non-Radiative Transitions of a Trapped Electron in a Crystal Kubo, Ryogo; Toyozawa, Yutaka Progress of Theoretical Physics, Vol. 13, Issue 2 https://doi.org/10.1143/PTP.13.160	journal	February 1955
A Critical Review of Li∕Air Batteries Christensen, Jake; Albertus, Paul; Sanchez-Carrera, Roel S. Journal of The Electrochemical Society, Vol. 159, Issue 2, p. R1-R30 https://doi.org/10.1149/2.086202jes	journal	January 2012

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