The hexaamminecobalt electron-exchange reaction

Ephraim Buhks; Mordechai Bixon; Joshua Jortner; Gil Navon

doi:10.1021/ic50197a059

The hexaamminecobalt electron-exchange reaction

Ephraim Buhks, Mordechai Bixon, Joshua Jortner, Gil Navon

School of Chemistry

Tel Aviv University

Research output: Contribution to journal › Article › peer-review

96 Scopus citations

Abstract

In this paper we present a theoretical study of the extraordinarily slow electron-exchange reaction Co³⁺(NH₃)₆ + Co²⁺(NH₃)₆Co²⁺(NH₃)₆ + Co³⁺(NH₃)₆. With the utilization of multiphonon theory fornonadiabatic electron-transfer reactions, ki was expressed as a product of a two-center electron-exchange term, K_if², and a nuclear Franck-Condon factor, G. K_if ² was evaluated by invoking the effects of spin-orbit coupling, while G was calculated by incorporating the effects of configurational changes and of frequency changes in the first coordination layer, as well as the Marcus-Levich solvent reorganizationenergy. We demonstrate that both electronic spin multiplicity restrictions and the nuclear reorganization energycontribute significantly to the retardation of the rate of this reaction. The mechanism considered herein is more efficient than the alternative reaction paths which involve thermally excited electronic states.

Original language	English
Pages (from-to)	2014-2018
Number of pages	5
Journal	Inorganic Chemistry
Volume	18
Issue number	7
DOIs	https://doi.org/10.1021/ic50197a059
State	Published - 1 Feb 1979

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abstract = "In this paper we present a theoretical study of the extraordinarily slow electron-exchange reaction Co3+(NH3)6 + Co2+(NH3)6Co2+(NH3)6 + Co3+(NH3)6. With the utilization of multiphonon theory fornonadiabatic electron-transfer reactions, ki was expressed as a product of a two-center electron-exchange term, Kif2, and a nuclear Franck-Condon factor, G. Kif 2 was evaluated by invoking the effects of spin-orbit coupling, while G was calculated by incorporating the effects of configurational changes and of frequency changes in the first coordination layer, as well as the Marcus-Levich solvent reorganizationenergy. We demonstrate that both electronic spin multiplicity restrictions and the nuclear reorganization energycontribute significantly to the retardation of the rate of this reaction. The mechanism considered herein is more efficient than the alternative reaction paths which involve thermally excited electronic states.",

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T1 - The hexaamminecobalt electron-exchange reaction

AU - Buhks, Ephraim

AU - Bixon, Mordechai

AU - Jortner, Joshua

AU - Navon, Gil

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N2 - In this paper we present a theoretical study of the extraordinarily slow electron-exchange reaction Co3+(NH3)6 + Co2+(NH3)6Co2+(NH3)6 + Co3+(NH3)6. With the utilization of multiphonon theory fornonadiabatic electron-transfer reactions, ki was expressed as a product of a two-center electron-exchange term, Kif2, and a nuclear Franck-Condon factor, G. Kif 2 was evaluated by invoking the effects of spin-orbit coupling, while G was calculated by incorporating the effects of configurational changes and of frequency changes in the first coordination layer, as well as the Marcus-Levich solvent reorganizationenergy. We demonstrate that both electronic spin multiplicity restrictions and the nuclear reorganization energycontribute significantly to the retardation of the rate of this reaction. The mechanism considered herein is more efficient than the alternative reaction paths which involve thermally excited electronic states.

AB - In this paper we present a theoretical study of the extraordinarily slow electron-exchange reaction Co3+(NH3)6 + Co2+(NH3)6Co2+(NH3)6 + Co3+(NH3)6. With the utilization of multiphonon theory fornonadiabatic electron-transfer reactions, ki was expressed as a product of a two-center electron-exchange term, Kif2, and a nuclear Franck-Condon factor, G. Kif 2 was evaluated by invoking the effects of spin-orbit coupling, while G was calculated by incorporating the effects of configurational changes and of frequency changes in the first coordination layer, as well as the Marcus-Levich solvent reorganizationenergy. We demonstrate that both electronic spin multiplicity restrictions and the nuclear reorganization energycontribute significantly to the retardation of the rate of this reaction. The mechanism considered herein is more efficient than the alternative reaction paths which involve thermally excited electronic states.

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The hexaamminecobalt electron-exchange reaction

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