Energetics of reactions involving transition metal complexes: Calculation of relative electrode potentials for cobalt complexes at various ionic strengths using density functional and Poisson-Boltzmann methods

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6 Citations (Scopus)

Abstract

A combination of nonlocal density functional calculations and the Poisson-Boltzmann method for the evaluation of free energies of hydration has been used to evaluate the electrode potential of [Co(NH3)6]3+ and [Co(en)3]3+ (where en = H2NCH2CH2NH2) using [Co(dien)2]3+ as a reference (where dien = H2NCH2CH2NHCH2CH2NH2). For [Co(en)3]3+, the electrode potential has been calculated to within 61 mV of the experimental value. For [Co(NH3)6]3+, the electrode potential is reproduced to within about 300 mV of experiment. The geometries of the complexes were optimized using the local spin density (LSD) method, with a LSD-optimized double-ζ plus polarization Gaussian basis set. Single-point nonlocal calculations were carried out at the optimized geometry using the Becke and Perdew combination of functionals for exchange and correlation to obtain both the energies and potential-derived charges. The potential-derived charges were used in the Poisson-Boltzmann calculations. The variation of the electrode potential of [Co(en)3]3+ with ionic strength is reproduced well. The suitability of the Poisson-Boltzmann method for treating hydration in these systems is critically assessed in light of the agreement between theory and experiment.

Original languageEnglish
Pages (from-to)10545-10550
Number of pages6
JournalJournal of the American Chemical Society
Volume118
Issue number43
DOIs
Publication statusPublished - 30 Oct 1996
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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