Computational electrochemistry: The aqueous Ru3+|Ru2+ reduction potential

Pablo Jaque, Aleksandr V. Marenich, Christopher J. Cramer, Donald G. Truhlar

Resultado de la investigación: Article

108 Citas (Scopus)

Resumen

We present results of density functional calculations for the standard reduction potential of the Ru3+|Ru2+ couple in aqueous solution. The metal cations are modeled as [Ru(H2O)n] q+ surrounded by continuum solvent (q = 2, 3; n = 6, 18). The continuum model includes bulk electrostatic polarization as well as atomic surface tensions accounting for the deviation of the second or third hydration shell from the bulk. After consideration of 37 density functionals with 5 different basis sets, it has been found that hybrid and hybrid meta functionals provide the most accurate predictions for the [Ru(H2O) n]q+ geometries and for the corresponding reduction potential in comparison with available experimental data. The gas-phase ionization potentials of [Ru(H2O)n]2+ calculated by density functional theory are also compared to results of ab initio computations using second-order Møller-Plesset perturbation theory. The difference in solvation free energies of Ru3+ and Ru 2+ varies from -10.56 to -10.99 eV for n = 6 and from -6.83 to -7.45 eV for n = 18 depending on the density functional and basis set quality. The aqueous standard reduction potential is overestimated when only the first solvation shell is treated explicitly and is underestimated when the first and second solvation shells are treated explicitly.

Idioma originalEnglish
Páginas (desde-hasta)5783-5799
Número de páginas17
PublicaciónJournal of Physical Chemistry C
Volumen111
N.º15
DOI
EstadoPublished - 19 abr 2007

Huella dactilar

Solvation
Electrochemistry
electrochemistry
solvation
functionals
Density functional theory
continuums
Ionization potential
ionization potentials
Hydration
Free energy
Surface tension
hydration
Cations
Electrostatics
interfacial tension
perturbation theory
Gases
Positive ions
Metals

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Citar esto

Jaque, P., Marenich, A. V., Cramer, C. J., & Truhlar, D. G. (2007). Computational electrochemistry: The aqueous Ru3+|Ru2+ reduction potential. Journal of Physical Chemistry C, 111(15), 5783-5799. https://doi.org/10.1021/jp066765w
Jaque, Pablo ; Marenich, Aleksandr V. ; Cramer, Christopher J. ; Truhlar, Donald G. / Computational electrochemistry : The aqueous Ru3+|Ru2+ reduction potential. En: Journal of Physical Chemistry C. 2007 ; Vol. 111, N.º 15. pp. 5783-5799.
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abstract = "We present results of density functional calculations for the standard reduction potential of the Ru3+|Ru2+ couple in aqueous solution. The metal cations are modeled as [Ru(H2O)n] q+ surrounded by continuum solvent (q = 2, 3; n = 6, 18). The continuum model includes bulk electrostatic polarization as well as atomic surface tensions accounting for the deviation of the second or third hydration shell from the bulk. After consideration of 37 density functionals with 5 different basis sets, it has been found that hybrid and hybrid meta functionals provide the most accurate predictions for the [Ru(H2O) n]q+ geometries and for the corresponding reduction potential in comparison with available experimental data. The gas-phase ionization potentials of [Ru(H2O)n]2+ calculated by density functional theory are also compared to results of ab initio computations using second-order M{\o}ller-Plesset perturbation theory. The difference in solvation free energies of Ru3+ and Ru 2+ varies from -10.56 to -10.99 eV for n = 6 and from -6.83 to -7.45 eV for n = 18 depending on the density functional and basis set quality. The aqueous standard reduction potential is overestimated when only the first solvation shell is treated explicitly and is underestimated when the first and second solvation shells are treated explicitly.",
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Jaque, P, Marenich, AV, Cramer, CJ & Truhlar, DG 2007, 'Computational electrochemistry: The aqueous Ru3+|Ru2+ reduction potential', Journal of Physical Chemistry C, vol. 111, n.º 15, pp. 5783-5799. https://doi.org/10.1021/jp066765w

Computational electrochemistry : The aqueous Ru3+|Ru2+ reduction potential. / Jaque, Pablo; Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.

En: Journal of Physical Chemistry C, Vol. 111, N.º 15, 19.04.2007, p. 5783-5799.

Resultado de la investigación: Article

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AU - Cramer, Christopher J.

AU - Truhlar, Donald G.

PY - 2007/4/19

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N2 - We present results of density functional calculations for the standard reduction potential of the Ru3+|Ru2+ couple in aqueous solution. The metal cations are modeled as [Ru(H2O)n] q+ surrounded by continuum solvent (q = 2, 3; n = 6, 18). The continuum model includes bulk electrostatic polarization as well as atomic surface tensions accounting for the deviation of the second or third hydration shell from the bulk. After consideration of 37 density functionals with 5 different basis sets, it has been found that hybrid and hybrid meta functionals provide the most accurate predictions for the [Ru(H2O) n]q+ geometries and for the corresponding reduction potential in comparison with available experimental data. The gas-phase ionization potentials of [Ru(H2O)n]2+ calculated by density functional theory are also compared to results of ab initio computations using second-order Møller-Plesset perturbation theory. The difference in solvation free energies of Ru3+ and Ru 2+ varies from -10.56 to -10.99 eV for n = 6 and from -6.83 to -7.45 eV for n = 18 depending on the density functional and basis set quality. The aqueous standard reduction potential is overestimated when only the first solvation shell is treated explicitly and is underestimated when the first and second solvation shells are treated explicitly.

AB - We present results of density functional calculations for the standard reduction potential of the Ru3+|Ru2+ couple in aqueous solution. The metal cations are modeled as [Ru(H2O)n] q+ surrounded by continuum solvent (q = 2, 3; n = 6, 18). The continuum model includes bulk electrostatic polarization as well as atomic surface tensions accounting for the deviation of the second or third hydration shell from the bulk. After consideration of 37 density functionals with 5 different basis sets, it has been found that hybrid and hybrid meta functionals provide the most accurate predictions for the [Ru(H2O) n]q+ geometries and for the corresponding reduction potential in comparison with available experimental data. The gas-phase ionization potentials of [Ru(H2O)n]2+ calculated by density functional theory are also compared to results of ab initio computations using second-order Møller-Plesset perturbation theory. The difference in solvation free energies of Ru3+ and Ru 2+ varies from -10.56 to -10.99 eV for n = 6 and from -6.83 to -7.45 eV for n = 18 depending on the density functional and basis set quality. The aqueous standard reduction potential is overestimated when only the first solvation shell is treated explicitly and is underestimated when the first and second solvation shells are treated explicitly.

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