title: Benchmark Calculations of Absolute Reduction Potential of Ferricinium/Ferrocene Couple in Nonaqueous Solutions.
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.
authors.affiliation: ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia.
authors.forename: Mansoor
authors.initials: M
authors.lastname: Namazian
authors.affiliation: ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia.
authors.forename: Ching Yeh
authors.initials: CY
authors.lastname: Lin
authors.affiliation: ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia.
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Coote