Accurate Calculation of Absolute One-Electron Redox Potentials of Some para-Quinone Derivatives in Acetonitrile

Mansoor Namazian, Michelle L. Coote

Research output: Contribution to journalArticlepeer-review

90 Citations (Scopus)

Abstract

Standard ab initio molecular orbital theory and density functional theory calculations have been used to calculate absolute one-electron reduction potentials of several para-quinones in acetonitrile. The high-level composite method of G3(MP2)-RAD is used for the gas-phase calculations and a continuum model of solvation, CPCM, has been employed to calculate solvation energies. To compare the theoretical reduction potentials with experiment, the reduction potentials relative to a standard calomel electrode (SCE) have also been calculated and compared to experimental values. The average error of the calculated reduction potentials using the proposed method is 0.07 V without any additional approximation. An ONIOM method in which the core is studied at G3(MP2)-RAD and the substituent effect of the rest of the molecule is studied at R(O)MP2/6-311+G(3df,-2p) provides an accurate low-cost alternative to G3(MP2)-RAD for larger molecules.

Original languageEnglish
Pages (from-to)7227-7232
Number of pages6
JournalJournal of Physical Chemistry A
Volume111
Issue number30
DOIs
Publication statusPublished - 1 Aug 2007
Externally publishedYes

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