Theory of the transition from sequential to concerted electrochemical proton-electron transfer.

A theory for the calculation of potential energy surfaces of electrochemical proton-coupled electron transfer is considered and parameterized on the basis of thermodynamic relations. The paper discusses the qualitatively different potential energy surfaces predicted by the theory, and their relation to the existence of sequential and concerted proton-electron transfer pathways. The concomitant activation energies for sequential and concerted PET are calculated. The applied overpotential may change the qualitative shape of the PES and therefore the mechanism of the proton-coupled electron transfer reaction.

[1]  J. Savéant,et al.  Electrochemical concerted proton and electron transfers. Potential-dependent rate constant, reorganization factors, proton tunneling and isotope effects , 2006 .

[2]  E. D. German,et al.  Theory of homogeneous reactions involving proton transfer , 1970 .

[3]  W. Schmickler.  A unified model for electrochemical electron and ion transfer reactions , 1995 .

[4]  Robert I. Cukier,et al.  Mechanism for Proton-Coupled Electron-Transfer Reactions , 1994 .

[5]  Photoluminescence spectra of self-assembling helical supramolecular assemblies: a theoretical study. , 2008, The journal of physical chemistry. B.

[6]  R. Marcus.  Enzymatic catalysis and transfers in solution. I. Theory and computations, a unified view. , 2006, The Journal of chemical physics.

[7]  Y. Hori,et al.  Selective Formation of C2 Compounds from Electrochemical Reduction of CO2 at a Series of Copper Single Crystal Electrodes , 2002 .

[8]  W. Schmickler.  A theory of adiabatic electron-transfer reactions , 1986 .

[9]  J. Grimminger,et al.  Dynamics of combined electron- and proton transfer at metal electrodes , 2007 .

[10]  S. Hammes-Schiffer,et al.  Theory of coupled electron and proton transfer reactions. , 2010, Chemical reviews.

[11]  Sharon Hammes-Schiffer,et al.  Current theoretical challenges in proton-coupled electron transfer: Electron-proton nonadiabaticity, proton relays, and ultrafast dynamics , 2011 .

[12]  A. Stuchebrukhov,et al.  Concerted electron and proton transfer: Transition from nonadiabatic to adiabatic proton tunneling , 2000 .

[13]  Christoph Hartnig,et al.  Solvent reorganization in electron and ion transfer reactions near a smooth electrified surface: a molecular dynamics study. , 2003, Journal of the American Chemical Society.

[14]  K. L. Sebastian.  Electrochemical electron transfer: Accounting for electron–hole excitations in the metal electrode , 1989 .

[15]  August W. Calhoun,et al.  Electrochemical Bond-Breaking Reactions: A Comparison of Large Scale Simulation Results with Analytical Theory , 1999 .

[16]  J. Mayer,et al.  Thermochemistry of proton-coupled electron transfer reagents and its implications. , 2010, Chemical reviews.

[17]  Stanley C. S. Lai,et al.  Electrocatalytic oxidation of alcohols on gold in alkaline media: base or gold catalysis? , 2011, Journal of the American Chemical Society.

[18]  A. Soudackov,et al.  Multidimensional treatment of stochastic solvent dynamics in photoinduced proton-coupled electron transfer processes: sequential, concerted, and complex branching mechanisms. , 2011, The Journal of chemical physics.

[19]  A. Kuznetsov,et al.  Theory of hydrogen-ion discharge on metals: Case of high overvoltages , 1968 .

[20]  C. Costentin.  Electrochemical approach to the mechanistic study of proton-coupled electron transfer. , 2008, Chemical reviews.

[21]  J. Grimminger,et al.  A model for combined electron and proton transfer in electrochemical systems , 2005 .

[22]  A. Soudackov,et al.  Model system-bath Hamiltonian and nonadiabatic rate constants for proton-coupled electron transfer at electrode-solution interfaces. , 2008, The Journal of chemical physics.

[23]  G. Voth,et al.  A theory for adiabatic bond breaking electron transfer reactions at metal electrodes , 1998 .

[24]  S. Hammes-Schiffer,et al.  Model Proton-Coupled Electron Transfer Reactions in Solution: Predictions of Rates, Mechanisms, and Kinetic Isotope Effects , 2000 .

[25]  J. Hynes,et al.  Electronic friction and electron transfer rates at metallic electrodes , 1993 .

[26]  M. Koper,et al.  Molecular dynamics simulations of solvent reorganization in electron-transfer reactions , 2001 .

[27]  J. Ulstrup,et al.  Proton and hydrogen atom tunnelling in hydrolytic and redox enzyme catalysis , 1999 .

[28]  Samantha Horvath,et al.  Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production , 2012, Proceedings of the National Academy of Sciences.

[29]  M. Koper,et al.  A theory for amalgam forming electrode reactions , 1998 .

[30]  Stanley C. S. Lai,et al.  Effects of electrolyte pH and composition on the ethanol electro-oxidation reaction , 2010 .

[31]  James M Mayer,et al.  Proton-coupled electron transfer: a reaction chemist's view. , 2004, Annual review of physical chemistry.

[32]  J. Ulstrup,et al.  Theory of Interrelated Electron and Proton Transfer Processes , 2003 .

[33]  P. Rodríguez,et al.  The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst. , 2012, Nature chemistry.

[34]  Rudolph A. Marcus,et al.  Theoretical relations among rate constants, barriers, and Broensted slopes of chemical reactions , 1968 .

[35]  J. Savéant,et al.  Concerted proton-electron transfer reactions in water. are the driving force and rate constant depending on pH when water acts as proton donor or acceptor? , 2007, Journal of the American Chemical Society.

[36]  A. Soudackov,et al.  Derivation of rate expressions for nonadiabatic proton-coupled electron transfer reactions in solution , 2000 .

[37]  S. Hammes-Schiffer,et al.  Theory of proton-coupled electron transfer in energy conversion processes. , 2009, Accounts of chemical research.

[38]  M. Koper,et al.  Nitrogen cycle electrocatalysis. , 2009, Chemical reviews.

[39]  M. Koper,et al.  Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. , 2012, Journal of the American Chemical Society.

[40]  M. Koper,et al.  Quantum effects in adiabatic electrochemical electron-transfer reactions , 1997 .

[41]  S. Hammes-Schiffer,et al.  Theoretical perspectives on proton-coupled electron transfer reactions. , 2001, Accounts of chemical research.

[42]  Jean-Michel Savéant,et al.  Concerted proton-electron transfers: electrochemical and related approaches. , 2010, Accounts of chemical research.

[43]  Philip W. Anderson,et al.  Localized Magnetic States in Metals , 1961 .

[44]  A. Soudackov,et al.  Multistate continuum theory for multiple charge transfer reactions in solution , 1999 .

[45]  R I Cukier,et al.  Proton-coupled electron transfer. , 1998, Annual review of physical chemistry.

[46]  Stanley C. S. Lai,et al.  The influence of solution-phase HNO2 decomposition on the electrocatalytic nitrite reduction at a hemin-pyrolitic graphite electrode. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[47]  Stanley C. S. Lai,et al.  New insights into the mechanism of nitrite reduction on a platinum electrode , 2010 .

[48]  M. Koper,et al.  Electrochemical reduction of carbon dioxide on copper electrodes , 2017 .

[49]  T. Meyer,et al.  Proton-coupled electron transfer. , 2007, Chemical reviews.

[50]  Mark N. Kobrak,et al.  Molecular dynamics simulation of proton-coupled electron transfer in solution , 2001 .

[51]  Ian J. Rhile,et al.  Thermodynamics and kinetics of proton-coupled electron transfer: stepwise vs. concerted pathways. , 2004, Biochimica et biophysica acta.

[52]  A. Soudackov,et al.  Nonadiabatic dynamics of photoinduced proton-coupled electron transfer: comparison of explicit and implicit solvent simulations. , 2012, The journal of physical chemistry. B.

[53]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. , 2004, The journal of physical chemistry. B.

[54]  S. Hammes-Schiffer,et al.  Proton-coupled electron transfer: classification scheme and guide to theoretical methods , 2012 .

[55]  Rudolph A. Marcus,et al.  On the Theory of Electron-Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions , 1965 .

[56]  D. M. Newns.  Self-Consistent Model of Hydrogen Chemisorption , 1969 .