Modeling Electron Transfer in Diffusive Multidimensional Electrochemical Systems

Coffman, Alec J.; Harshan, Aparna Karippara; Hammes‐Schiffer, Sharon; Subotnik, Joseph E.

doi:10.1021/acs.jpcc.9b02068

Cited by 5 publications

(2 citation statements)

References 50 publications

(59 reference statements)

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“…Additionally, the quantum mechanical electronic coupling between the reactive species and the band orbitals of the electrode changes significantly with z , serving to facilitate ET near an electrode surface. A recent study incorporated an approach coordinate to examine the interaction between interfacial ET and macroscopic transport processes in electrochemical devices . In contrast, our model allows us to understand the influence of microscopic property variations and diffusive transport on interfacial ET.…”

Section: Smoluchowski Master Equation (Sme) Modelmentioning

confidence: 99%

“…A recent study incorporated an approach coordinate to examine the interaction between interfacial ET and macroscopic transport processes in electrochemical devices. 24 In contrast, our model allows us to understand the influence of microscopic property variations and diffusive transport on interfacial ET. Hence, the approach coordinate in this model is resolved within a length scale L representing the spatial extent of the EDL, most closely associated with the Debye screening length of the electrolyte.…”

Section: ■ Introductionmentioning

confidence: 99%

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Modeling Interfacial Electron Transfer in the Double Layer: The Interplay between Electrode Coupling and Electrostatic Driving

Limaye

Willard

2019

J. Phys. Chem. C

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In this manuscript we present a theoretical model for studying the population dynamics of electrochemical systems within the region of the electrical double layer. We formulate this model in a coordinate system that separately resolves both the transport of redox species in the direction perpendicular to the electrode surface and the thermal fluctuations of the solvent environment that drive electron transfer. This formulation enables us to explore how the observable characteristics of electrochemical systems are influenced by spatial variations in the electric fields and electronic couplings that are inherent to the double-layer. We apply this model to highlight the fundamental interplay between two physical attributes of interfacial electrochemistry: electrode coupling and electrostatic driving. Using a simple model system we demonstrate how variations in the location of electron transfer can lead to systematic changes to the electrochemical transfer coefficient. We also illustrate that for certain redox reactions, differences in electrostatic driving between products and reactants can lead to non-monotonic current voltage behavior.

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Section: Smoluchowski Master Equation (Sme) Modelmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Modeling Interfacial Electron Transfer in the Double Layer: The Interplay between Electrode Coupling and Electrostatic Driving

Limaye

Willard

2019

J. Phys. Chem. C

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Modeling voltammetry curves for proton coupled electron transfer: The importance of nuclear quantum effects

Coffman

Dou

Hammes‐Schiffer

et al. 2020

The Journal of Chemical Physics

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We investigate rates of proton-coupled electron transfer (PCET) in potential sweep experiments for a generalized Anderson–Holstein model with the inclusion of a quantized proton coordinate. To model this system, we utilize a quantum classical Liouville equation embedded inside of a classical master equation, which can be solved approximately with a recently developed algorithm combining diffusional effects and surface hopping between electronic states. We find that the addition of nuclear quantum effects through the proton coordinate can yield quantitatively (but not qualitatively) different IV curves under a potential sweep compared to electron transfer (ET). Additionally, we find that kinetic isotope effects give rise to a shift in the peak potential, but not the peak current, which would allow for quantification of whether an electrochemical ET event is proton-coupled or not. These findings suggest that it will be very difficult to completely understand coupled nuclear–electronic effects in electrochemical voltammetry experiments using only IV curves, and new experimental techniques will be needed to draw inferences about the nature of electrochemical PCET.

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Physics applied to electrochemistry: Tunneling reactions

Bevan

Foong

Shirani

et al. 2021

Journal of Applied Physics

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In this work, we explore how electrochemical tunneling reactions can be understood within the single-particle picture. That is, the formal approach in which band diagrams are typically utilized to understand electronic processes in solid-state materials and devices. This single-particle perspective is based upon the Gerischer–Hopfield description of electron transfer at solid–liquid interfaces. Both single and multiple electron tunneling reactions are discussed, as are related voltammetric concepts and trends. The impact of nuclear quantization on the Gerischer–Hopfield description is also addressed, as well as its compact representation of two probe electrochemical phenomena at low temperatures (often referred to as Franck–Condon blockade). In this manner, a perspective linking solid-state phenomena and tunneling electrochemical reactions is presented.

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Modeling Electron Transfer in Diffusive Multidimensional Electrochemical Systems

Cited by 5 publications

References 50 publications

Modeling Interfacial Electron Transfer in the Double Layer: The Interplay between Electrode Coupling and Electrostatic Driving

Modeling Interfacial Electron Transfer in the Double Layer: The Interplay between Electrode Coupling and Electrostatic Driving

Modeling voltammetry curves for proton coupled electron transfer: The importance of nuclear quantum effects

Physics applied to electrochemistry: Tunneling reactions

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