### Resumen

We present results of density functional calculations for the standard reduction potential of the Ru^{3+}|Ru^{2+} couple in aqueous solution. The metal cations are modeled as [Ru(H_{2}O)_{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(H_{2}O) _{n}]^{q+} geometries and for the corresponding reduction potential in comparison with available experimental data. The gas-phase ionization potentials of [Ru(H_{2}O)_{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 Ru^{3+} 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 original | English |
---|---|

Páginas (desde-hasta) | 5783-5799 |

Número de páginas | 17 |

Publicación | Journal of Physical Chemistry C |

Volumen | 111 |

N.º | 15 |

DOI | |

Estado | Published - 19 abr 2007 |

### Huella dactilar

### ASJC Scopus subject areas

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

### Citar esto

^{3+}|Ru

^{2+}reduction potential.

*Journal of Physical Chemistry C*,

*111*(15), 5783-5799. https://doi.org/10.1021/jp066765w

}

^{3+}|Ru

^{2+}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 Ru ^{3+}|Ru^{2+} reduction potential.** / Jaque, Pablo; Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.

Resultado de la investigación: Article

TY - JOUR

T1 - Computational electrochemistry

T2 - The aqueous Ru3+|Ru2+ reduction potential

AU - Jaque, Pablo

AU - Marenich, Aleksandr V.

AU - Cramer, Christopher J.

AU - Truhlar, Donald G.

PY - 2007/4/19

Y1 - 2007/4/19

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.

UR - http://www.scopus.com/inward/record.url?scp=34247615474&partnerID=8YFLogxK

U2 - 10.1021/jp066765w

DO - 10.1021/jp066765w

M3 - Article

AN - SCOPUS:34247615474

VL - 111

SP - 5783

EP - 5799

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 15

ER -

^{3+}|Ru

^{2+}reduction potential. Journal of Physical Chemistry C. 2007 abr 19;111(15):5783-5799. https://doi.org/10.1021/jp066765w