The reversible one-electron oxidation of Ferrocene (Fc) → Ferrocenium (Fc+) is commonly used as a standard in electrochemistry where the Fc/Fc+ couple is about 0.40 V, relative to the standard hydrogen electrode (SHE). Electronic structure methods have been extensively used to quantify the redox potentials of numerous electron transfer processes, both in gas as well as the condensed phase. However, the exact magnitude of the redox potential of the Fc+/Fc couple in the condensed phase is not well ascertained, due to complexities involved in modeling the solvent environment, as well as the proximity of low-lying electronic excited states in the Ferrocenium molecule.<br/><br/>Here we model the redox potential of the Fc/Fc+ couple in the condensed phase, using a combination of classical molecular dynamics simulations as well as polarizable QM/MM methods that accurately represent the Fc/Fc+ one electron ionization in its solution phase. Our current results indicate that despite the presence of static correlation in the Ferrocenium molecule, various wavefunction-based DFT methods can accurately model the oxidation of Fc → Fc+ in acetonitrile solvent. Further, implicit solvent models fail to describe the short-range solvent effects, necessitating the explicit inclusion of solvent molecules in the quantum Hamiltonian. Our studies also indicate that the solvation structure of Ferrocene is better represented using molecular dynamics simulation methods with the explicit inclusion of polarization.

Standardizing the standard ferrocene-ferrocenium redox couple: Modeling redox potentials in the condensed phase using multiscale QM/MM methods

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.