Benchmark Calculations of Absolute Reduction Potential of Ferricinium/Ferrocene Couple in Nonaqueous Solutions

Mansoor Namazian, Ching Yeh Lin, Michelle L. Coote

Research output: Contribution to journalArticlepeer-review

141 Citations (Scopus)

Abstract

High-level ab initio molecular orbital theory is used to obtain benchmark values for the ferricenium/ferrocene (Fc+/Fc) couple, the IUPAC recommended reference electrode for nonaqueous solution. The gas-phase ionization energy of ferrocene is calculated using the high-level composite method, G3(MP2)-RAD, and two higher-level variants of this method. These latter methods incorporate corrections for core correlation and, in the case of the highest level considered, use (RO)CCSD(T)/6-311+G(d,p) in place of (RO)CCSD(T)/6-31G(d) as the base level of theory. All methods provide good agreement with one another and the corresponding experimental values. Solvation energies have been calculated using PCM, CPCM, SMD, and COSMO-RS. Using G3(MP2)-RAD-Full-TZ gas-phase energies and COSMO-RS solvation energies, the absolute redox potentials of the Fc+/Fc couple have been calculated as 4.988, 4.927, and 5.043 V in acetonitrile, 1,2-dichloroethane, and dimethylsulfoxide solutions, respectively.

Original languageEnglish
Pages (from-to)2721-2725
Number of pages5
JournalJournal of Chemical Theory and Computation
Volume6
Issue number9
DOIs
Publication statusPublished - 14 Sep 2010
Externally publishedYes

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