Quantum Chemical Study of the Redox Potential of the Co(OH2)6 2+/3+ Couple and the Singlet-Quintet Gibbs Energy Difference of the Co(OH2)6 3+ Ion

François P. Rotzinger, Hui Li

Research output: Contribution to journalArticle

Abstract

The geometry and vibrational frequencies of Co(OH2)6 2+ in the quartet state and Co(OH2)6 3+ in the singlet and quintet states were computed with quantum mechanics/molecular mechanics (QM/MM), whereby the LC-BOP-LRD functional was used for the QM part involving the Co(OH2)6 n+ (n = 2, 3) ions. The surrounding 124 MM water molecules were treated with the MMFF94 force field. The hydration energy differences between low-spin Co(OH2)6 3+ and Co(OH2)6 2+ or Co(OH2)6 3+ in the quintet state were also calculated using this method. The electronic energy of the Co(OH2)6 n+ (n = 2, 3) ions was calculated with wave function theory, multistate extended general multiconfiguration quasi-degenerate second-order perturbation theory and spin-orbit configuration interaction. The redox potential of the Co(OH2)6 2+/3+ couple, and the singlet-quintet (adiabatic) Gibbs energy difference of Co(OH2)6 3+, computed based on these data, agree with the experiment.

Original languageEnglish (US)
Pages (from-to)10122-10127
Number of pages6
JournalInorganic Chemistry
Volume57
Issue number16
DOIs
StatePublished - Aug 20 2018

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Gibbs free energy
Ions
Molecular mechanics
Quantum theory
Vibrational spectra
Wave functions
Hydration
ions
Orbits
field theory (physics)
configuration interaction
Molecules
hydration
Geometry
energy
Water
quantum mechanics
perturbation theory
wave functions
orbits

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Quantum Chemical Study of the Redox Potential of the Co(OH2)6 2+/3+ Couple and the Singlet-Quintet Gibbs Energy Difference of the Co(OH2)6 3+ Ion. / Rotzinger, François P.; Li, Hui.

In: Inorganic Chemistry, Vol. 57, No. 16, 20.08.2018, p. 10122-10127.

Research output: Contribution to journalArticle

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abstract = "The geometry and vibrational frequencies of Co(OH2)6 2+ in the quartet state and Co(OH2)6 3+ in the singlet and quintet states were computed with quantum mechanics/molecular mechanics (QM/MM), whereby the LC-BOP-LRD functional was used for the QM part involving the Co(OH2)6 n+ (n = 2, 3) ions. The surrounding 124 MM water molecules were treated with the MMFF94 force field. The hydration energy differences between low-spin Co(OH2)6 3+ and Co(OH2)6 2+ or Co(OH2)6 3+ in the quintet state were also calculated using this method. The electronic energy of the Co(OH2)6 n+ (n = 2, 3) ions was calculated with wave function theory, multistate extended general multiconfiguration quasi-degenerate second-order perturbation theory and spin-orbit configuration interaction. The redox potential of the Co(OH2)6 2+/3+ couple, and the singlet-quintet (adiabatic) Gibbs energy difference of Co(OH2)6 3+, computed based on these data, agree with the experiment.",
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