Electrode Reactions in Slowly Relaxing Media

Matyushov, Dmitry V.; Newton, Marshall D.

doi:10.1063/1.5003022

Title: Electrode Reactions in Slowly Relaxing Media

Journal Article · Fri Nov 17 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5003022· OSTI ID:1407474

Matyushov, Dmitry V. ^[1]; Newton, Marshall D. ^[2]

Arizona State Univ., Tempe, AZ (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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.

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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:: 1407474

Alternate ID(s):: OSTI ID: 1420660

Report Number(s):: BNL-114501-2017-JA; R&D Project: CO037; KC0304030; TRN: US1703050

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 19; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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Journal Article · Fri Apr 14 00:00:00 EDT 2006 · Journal of Chemical Physics · OSTI ID:1407474

Ghorai, Pradip K; Matyushov, Dmitry V

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75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electrode Reactions in Slowly Relaxing Media

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