On calculating reorganization energies for electrochemical reactions using density functional theory and continuum solvation models

Buda, Mihai

doi:10.1016/j.electacta.2013.09.045

Cited by 16 publications

(15 citation statements)

References 153 publications

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“…The average change in the Cu−O bond length is 0.074 Å, and the average change in the Mayer bond order between 2 and 2+ is 0.09 (Table S1); thus, these differences in covalency and coupling result from the nature of the bridge in 2 versus 2+ being O 2− vs O •− , respectively, rather than structural differences. To emphasize the point, the Marcus reorganization energy (λ inner ) 81 of the 2 → 2 + oxidation (Table S2) was calculated (see Supporting Information) 82 and found to be 0.143 eV. This small value is on the order of the experimentally measured Fc → Fc + λ inner of ∼0.1 eV 83,84 and much smaller than the already small λ inner reported by Karlin and co-workers for [Cu (II)…”

Section: Results and Analysismentioning

confidence: 79%

Exceptionally High O–H Bond Dissociation Free Energy of a Dicopper(II) μ-Hydroxo Complex and Insights into the Geometric and Electronic Structure Origins Thereof

et al. 2020

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The strength of the relevant bonds in bond-making and bond-breaking processes can directly affect the overall efficiency of the process. Copper–oxygen sites are known to catalyze reactions with some of the most recalcitrant C–H bonds found in nature as quantified by the bond dissociation free energy (BDFE), yet only a handful of copper-bound O–H bond strengths have been defined. Equally important in the design of synthetic catalysts is an understanding of the geometric and electronic structure origins of these thermodynamic parameters. In this report, the BDFE(OH) of two dicopper–hydroxo complexes, {[LCu]2-(μ-OH)}3+ and {[LCu]2-(μ-OH)}4+ (L = tris(2-pyridylmethyl)amine), were measured. Two key observations were made: (i) the BDFE(OH)s of these complexes were exceptionally high at 103.4 and 91.7 kcal/mol, respectively, which are the highest condensed phase MO-H BDFEs to date and (ii) that the higher oxidation state had a lower BDFE(OH), which is counter to expectations based on known mononuclear BDFE(OH)s which increase with the oxidation state. To understand the origin of these thermodynamic values, the BDFE(OH)s were measured and analyzed for the mononuclear complexes [LCu(OH2)]1+ and [LCu(OH2)]2+ in the same ligand environment. This treatment revealed “dinuclear effects” that include contributions from rehybridization of the oxygen, mixed valency of the metals, magnetic exchange between the metals, and differences in solvation, which are general with respect to [M]2–OH complexes to varying degrees. These analyses are important because they provide a starting point for rationally tuning the thermodynamics of catalytic intermediates broadly and for understanding how copper active sites achieve activation of strong C–H bonds.

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Section: Results and Analysismentioning

confidence: 79%

Exceptionally High O–H Bond Dissociation Free Energy of a Dicopper(II) μ-Hydroxo Complex and Insights into the Geometric and Electronic Structure Origins Thereof

et al. 2020

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“…22 In the absence of the thiol layer, the DmFc 0/+ process is reported to have large k 0 (>1 cm/s) 23 and small λ (∼0.8 eV) values in dimethylformamide (0.1 M tetrabutylammonium hexafluorophosphate). 24 Importantly, the bulky methyl groups on the two cyclopentadienyl rings can minimize the probability of DmFc penetrating into the monolayer layer (pinhole effect). The use of FTACV provides access to data on a widely varying time scale from a single experiment, 25 which provides information needed (up to six harmonics) to distinguish the two models.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The electron transfer reaction associated with ferrocene (Fc) and derivatives such as DmFc represents a widely studied outer-sphere electron process . In the absence of the thiol layer, the DmFc 0/+ process is reported to have large k 0 (>1 cm/s) and small λ (∼0.8 eV) values in dimethylformamide (0.1 M tetrabutylammonium hexafluorophosphate ) . Importantly, the bulky methyl groups on the two cyclopentadienyl rings can minimize the probability of DmFc penetrating into the monolayer layer (pinhole effect).…”

Section: Introductionmentioning

confidence: 99%

Demonstration of Superiority of the Marcus–Hush Electrode Kinetic Model in the Electrochemistry of Dissolved Decamethylferrocene at a Gold-Modified Electrode by Fourier-Transformed Alternating Current Voltammetry

Kennedy

Bond

2018

J. Phys. Chem. C

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Fourier-transformed alternating current (AC) voltammetry is used to compare the applicability of the Butler−Volmer (BV) and Marcus−Hush (MH) models of electrode kinetics (k 0 ) to an outer-sphere electrode process where both oxidized and reduced species are soluble. According to numerical simulations, differences between the two models can be revealed clearly by analysis of the AC harmonics when the values of k 0 and reorganization energy are sufficiently small. Experimentally a Au electrode coated with a self-assembled octanethiol monolayer was introduced to decrease the rate of the DmFc 0/+ (DmFc = decamethylferrocene) process, a well-known outer-sphere process in a propylene carbonate solution containing 0.10 M tetrapropylammonium tetrafluoroborate. Based on a comparison of the computationally generated best fits, it was demonstrated that the MH model provides substantially better agreement with the experimental data than the BV model for the DmFc 0/+ process, unlike some other examples in the literature that favor the BV model.

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“…70 Another implicit solvent calculation study by Buda showed that values of 35%-100% can be observed for smaller organic molecules in various organic or aqueous solvents. 79 In contrast, the 𝜆 % /𝜆 values determined by experimental spectroscopy for 1 st -row transition metal ions in aqueous solution are in a significantly lower range of 11%-39%. 77 Despite the wide range of 𝜆 % /𝜆 values reported, most computational studies of 𝜆 % focus on a small set of systems, or use implicit solvent calculations based on geometry-optimized structures without configuration sampling, due to computational challenge in QM or QM/MM configuration sampling for a large number of explicitly solvated systems.…”

Section: Application On Reorganization Energy Calculationmentioning

confidence: 96%

“…This range is on the lower end of the abovementioned computational literature results, but the solutes investigated in our data set are different, and our calculations are based on explicit solvent configuration sampling instead of implicit solvent-based protocol. 70,79 In addition, the outer-sphere contributions in Fig. 10 could be overestimated due to using non-polarizable solvent force field, which often underestimates the impact of solvent polarization.…”

Section: Application On Reorganization Energy Calculationmentioning

confidence: 99%

AutoSolvate: A Toolkit for Automating Quantum Chemistry Design and Discovery of Solvated Molecules

Hruska

Gale

Huang

et al. 2022

Preprint

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The availability of large, high-quality data sets is crucial for artificial intelligence design and discovery in chemistry. Despite the essential roles of solvents in chemistry, the rapid computational data set generation of solution-phase molecular properties at the quantum mechanical level of theory was previously hampered by the complicated simulation procedure. Software toolkits that can automate the procedure to set up high-throughput explicit-solvent quantum chemistry (QC) calculations for arbitrary solutes and solvents in an open-source framework are still lacking. We developed AutoSolvate, an open-source toolkit to streamline the workflow for QC calculation of explicitly solvated molecules. It automates the solvated-structure generation, force field fitting, configuration sampling, and the final extraction of microsolvated cluster structures that QC packages can readily use to predict molecular properties of interest. AutoSolvate is available through both a command line interface and a graphical user interface, making it accessible to the broader scientific community. To improve the quality of the initial structures generated by AutoSolvate, we investigated the dependence of solute-solvent closeness on solute/solvent identities and trained a machine learning model to predict the closeness and guide initial structure generation. Finally, we tested the capability of AutoSolvate for rapid data set curation by calculating the outer-sphere reorganization energy of a large data set of 166 redox couples, which demonstrated the promise of the AutoSolvate package for chemical discovery efforts.

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On calculating reorganization energies for electrochemical reactions using density functional theory and continuum solvation models

Cited by 16 publications

References 153 publications

Exceptionally High O–H Bond Dissociation Free Energy of a Dicopper(II) μ-Hydroxo Complex and Insights into the Geometric and Electronic Structure Origins Thereof

Exceptionally High O–H Bond Dissociation Free Energy of a Dicopper(II) μ-Hydroxo Complex and Insights into the Geometric and Electronic Structure Origins Thereof

Demonstration of Superiority of the Marcus–Hush Electrode Kinetic Model in the Electrochemistry of Dissolved Decamethylferrocene at a Gold-Modified Electrode by Fourier-Transformed Alternating Current Voltammetry

AutoSolvate: A Toolkit for Automating Quantum Chemistry Design and Discovery of Solvated Molecules

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