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 journalArticlepeer-review

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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