Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model

Ghosh, Soumya; Horvath, Samantha; Soudackov, Alexander V.; Hammes‐Schiffer, Sharon

doi:10.1021/ct500051e

Cited by 47 publications

(85 citation statements)

References 99 publications

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“…is 0.82 eV with λ i as small as 0.08 eV. It should be noted that the computed λ values lack a contribution from the interaction with the electrode and are likely to be overestimated by 0.2–0.4 eV …”

Section: Resultsmentioning

confidence: 89%

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On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches

et al. 2017

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In this work, sampled‐current voltammetry performed on a series of aryldiazonium, diaryliodonium, and triarylsulfonium salts allows the determination of the reduction potential of aryl radicals in acetonitrile. Specifically, this is accomplished by measuring the number of electrons consumed in the reduction process as a function of the applied potential. For the phenyl, 4‐bromophenyl, and 4‐nitrophenyl radicals, the reduction potential is found to be −0.91±0.06, −0.90±0.10, and −0.98±0.06 V vs. SCE, respectively. Furthermore, from measurements on an extended series of substituted compounds, it is concluded that the substituent effect on the reduction potential is small, which can be explained by the σ nature of the aryl radical as evidenced from theoretical calculations. At the same time this yields a mean value for the reduction potential of the aryl radical of −0.87 V±0.03 V vs. SCE. Determination of the intrinsic barrier and the standard potential from the data obtained are more uncertain since it is unknown to which extent the competing reference reaction, the electrochemical grafting reaction, is affected by the applied potential. From calculations using density functional theory, the intrinsic barrier for the reduction of the phenyl radical is determined to be 0.32 eV.

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Section: Resultsmentioning

confidence: 89%

“…Reorganization energies have been estimated following the approach developed by Hammes‐Schiffer and coworkers ,. The total reorganization energy is given by Equation .

true λ_{tot} = 0.5 (λ_{red} + λ_{ox})

…”

Section: Methodsmentioning

confidence: 99%

On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches

et al. 2017

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“…The electronic component of the solvent polarization is evaluated self-consistently with the solute charge density, denoted the self-consistent (SC) limit, using an algorithm reported elsewhere. 22 The total outer-sphere reorganization energy is the average of the outer-sphere reorganization energies calculated for reduction and oxidation of a redox molecule at the electrode.…”

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confidence: 99%

“…In the matrix-inversion formulation of the IEF-PCM, the surface charge density is determined by the solution of a matrix equation 22 that depends on the electrostatic potential at the center of each tessera induced by the solute charge density, as well as matrices related to the Green's functions and their normal derivatives inside and outside of the cavity. The matrix elements of the S E and D E matrices, which are related to the Green's function and its normal derivative, respectively, outside of the cavity are …”

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confidence: 99%

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Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes

Ghosh

Hammes‐Schiffer

2014

J. Phys. Chem. Lett.

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Electrochemical electron transfer reactions play an important role in energy conversion processes with many technological applications. Electrodes modified by self-assembled monolayers (SAMs) exhibit reduced double layer effects and are used in molecular electronics. An important quantity for calculating the electron transfer rate constant is the reorganization energy, which is associated with changes in the solute geometry and the environment. In this Letter, an approach for calculating the electrochemical reorganization energy for a redox molecule attached to or near a SAM modified electrode is presented. This integral equations formalism polarizable continuum model (IEF-PCM) approach accounts for the detailed electronic structure of the molecule, as well as the contributions from the electrode, SAM, and electronic and inertial solvent responses. The calculated total reorganization energies are in good agreement with experimental data for a series of metal complexes in aqueous solution. This approach will be useful for calculating electron transfer rate constants for molecular electrocatalysts.

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Nanoelectrochemistry of Adsorption‐Coupled Electron Transfer at Carbon Electrodes

Amemiya

2019

Nanocarbon Electrochemistry

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Electrochemical Solvent Reorganization Energies in the Framework of the Polarizable Continuum Model

Cited by 47 publications

References 99 publications

On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches

On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches

Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes

Nanoelectrochemistry of Adsorption‐Coupled Electron Transfer at Carbon Electrodes

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