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Benchmark calculations of absolute reduction potential of Ferricinium/Ferrocene couple in nonaqueous solutions

Namazian, Mansoor; Lin, Ching-Yeh; Coote, Michelle

Description

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...[Show more]

dc.contributor.authorNamazian, Mansoor
dc.contributor.authorLin, Ching-Yeh
dc.contributor.authorCoote, Michelle
dc.date.accessioned2015-12-10T22:57:51Z
dc.identifier.issn0219-6336
dc.identifier.urihttp://hdl.handle.net/1885/60618
dc.description.abstractHigh-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.
dc.publisherSingapore University Press and World Scientific Publishing Co Pty Ltd
dc.sourceJournal of Theoretical and Computational Chemistry
dc.titleBenchmark calculations of absolute reduction potential of Ferricinium/Ferrocene couple in nonaqueous solutions
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume6
dc.date.issued2010
local.identifier.absfor030399 - Macromolecular and Materials Chemistry not elsewhere classified
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationu4217927xPUB551
local.type.statusPublished Version
local.contributor.affiliationNamazian, Mansoor, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationLin, Ching-Yeh, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationCoote, Michelle, College of Physical and Mathematical Sciences, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.issue9
local.bibliographicCitation.startpage2721
local.bibliographicCitation.lastpage2725
local.identifier.doi10.1021/ct1003252
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
dc.date.updated2015-12-10T08:01:43Z
local.identifier.scopusID2-s2.0-77956565844
local.identifier.thomsonID000281693000014
CollectionsANU Research Publications

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