Modeling Absolute Redox Potentials of Ferrocene in the Condensed Phase

Małgorzata Zofia Makoś; Pradeep Kumar Gurunathan; Simone Raugei; Karol Kowalski; Vassiliki Alexandra Glezakou; Roger Rousseau

doi:10.1021/acs.jpclett.2c02447

Modeling Absolute Redox Potentials of Ferrocene in the Condensed Phase

Małgorzata Zofia Makoś, Pradeep Kumar Gurunathan, Simone Raugei, Karol Kowalski, Vassiliki Alexandra Glezakou, Roger Rousseau

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Absolute thermodynamic quantities for critical chemical reactions are needed to determine the role of solvents and reactive environments in catalysis and electrocatalysis. Theoretical methods can provide such quantification but are often hindered by the innate complexity of electron correlation and dynamic relaxation of solvent environments. We present and validate a protocol for calculating the redox potentials of the ferrocene/ferrocenium redox pair in acetonitrile. Equation-of-motion and effective fragment potential (EFP) methods are used to characterize the adiabatic and vertical ionization potentials as well as the electron affinity processes. We benchmark molecular mechanics against the EFP model to show the differences in the ferrocene electronic polarizability in two redox states. Our best estimate of the redox potential (4.94 eV) agrees well with the experimental value (4.93 eV). This demonstrates the ability of modern computational methods to predict absolute redox potentials quantitatively and to quantify the correlation of dynamic effects, which underlie their origin.

Original language	English
Pages (from-to)	10005-10010
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	13
Issue number	42
DOIs	https://doi.org/10.1021/acs.jpclett.2c02447
State	Published - Oct 27 2022
Externally published	Yes

Funding

M.Z.M., P.K.G., V.-A.G., and R.R. acknowledge support from the U.S. Department of Energy (DOE) Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences and Biosciences under FWP47319. S.R. was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by DOE, Office of Science, Office of Basic Energy Sciences. K.K. acknowledges support from the Center for Scalable Predictive methods for Excitations and Correlated phenomena (SPEC), which is funded by DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, as part of the Computational Chemical Sciences Program at Pacific Northwest National Laboratory. Computer resources were provided by the National Energy Research Center (NERSC) located at LBNL and the PNNL Research Computing facility. Pacific Northwest National Laboratory is operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Funders	Funder number
Center for Molecular Electrocatalysis
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Pacific Northwest National Laboratory	DE-AC05-76RL01830
Chemical Sciences, Geosciences, and Biosciences Division	FWP47319

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10.1021/acs.jpclett.2c02447

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abstract = "Absolute thermodynamic quantities for critical chemical reactions are needed to determine the role of solvents and reactive environments in catalysis and electrocatalysis. Theoretical methods can provide such quantification but are often hindered by the innate complexity of electron correlation and dynamic relaxation of solvent environments. We present and validate a protocol for calculating the redox potentials of the ferrocene/ferrocenium redox pair in acetonitrile. Equation-of-motion and effective fragment potential (EFP) methods are used to characterize the adiabatic and vertical ionization potentials as well as the electron affinity processes. We benchmark molecular mechanics against the EFP model to show the differences in the ferrocene electronic polarizability in two redox states. Our best estimate of the redox potential (4.94 eV) agrees well with the experimental value (4.93 eV). This demonstrates the ability of modern computational methods to predict absolute redox potentials quantitatively and to quantify the correlation of dynamic effects, which underlie their origin.",

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AU - Makoś, Małgorzata Zofia

AU - Gurunathan, Pradeep Kumar

AU - Raugei, Simone

AU - Kowalski, Karol

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

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N2 - Absolute thermodynamic quantities for critical chemical reactions are needed to determine the role of solvents and reactive environments in catalysis and electrocatalysis. Theoretical methods can provide such quantification but are often hindered by the innate complexity of electron correlation and dynamic relaxation of solvent environments. We present and validate a protocol for calculating the redox potentials of the ferrocene/ferrocenium redox pair in acetonitrile. Equation-of-motion and effective fragment potential (EFP) methods are used to characterize the adiabatic and vertical ionization potentials as well as the electron affinity processes. We benchmark molecular mechanics against the EFP model to show the differences in the ferrocene electronic polarizability in two redox states. Our best estimate of the redox potential (4.94 eV) agrees well with the experimental value (4.93 eV). This demonstrates the ability of modern computational methods to predict absolute redox potentials quantitatively and to quantify the correlation of dynamic effects, which underlie their origin.

AB - Absolute thermodynamic quantities for critical chemical reactions are needed to determine the role of solvents and reactive environments in catalysis and electrocatalysis. Theoretical methods can provide such quantification but are often hindered by the innate complexity of electron correlation and dynamic relaxation of solvent environments. We present and validate a protocol for calculating the redox potentials of the ferrocene/ferrocenium redox pair in acetonitrile. Equation-of-motion and effective fragment potential (EFP) methods are used to characterize the adiabatic and vertical ionization potentials as well as the electron affinity processes. We benchmark molecular mechanics against the EFP model to show the differences in the ferrocene electronic polarizability in two redox states. Our best estimate of the redox potential (4.94 eV) agrees well with the experimental value (4.93 eV). This demonstrates the ability of modern computational methods to predict absolute redox potentials quantitatively and to quantify the correlation of dynamic effects, which underlie their origin.

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Modeling Absolute Redox Potentials of Ferrocene in the Condensed Phase

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