Electrode reactions in slowly relaxing media

We address electrode reactions in this picture as an important class of reactions for which the electrode potential becomes a control parameter which can potentially drive the reaction out of ergodicity

Dmitry V. Matyushov


Scholarcy highlights

  • The theory of nonadiabatic electron transfer at metal electrodes has been established in theoretical work by Marcus, Hush,3 and Levich4 and extensively tested by a number of seminal experimental studies by Chidsey,5 Finklea,6 and Saveant.7 Nonadiabatic rate is calculated from the Golden-Rule perturbation theory for individual electronic transitions between the localized electronic state in solution and delocalized conduction states in the metal electrode.35810 The Golden-Rule expression is limited by a low magnitude of the electrode-reactant electronic coupling
  • We model electrode reactions3538 in room-temperature ionic liquids
  • The model presented here deals with the consequences of reaction nonergodicity for electrode reactions in media with sufficiently slow relaxation such that the relaxation time and the reaction time are comparable in magnitude
  • This condition leads to breaking of ergodicity for the statistics of configurations in the reactant and product wells
  • The problem is circumvented by defining Gibbs-weighted averages on a restricted sub-space of the entire phase space of the system
  • The statistical averages are calculated with the BoltzmannGibbs weights within a subspace Γ
  • It slowly changes when the reaction rate is altered over several orders of magnitude, to electron transfer in proteins.46 The phenomenology found here seems to be quite general and there are significant reasons to believe that this picture should be common to a number of materials with stretched exponential dynamics

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