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- W2073219145 abstract "Abstract The ferrocene/ferrocenium self-exchange electron-transfer reaction in the gas phase at 350 K is modelled by using statistical rate theory. The RRKM formulation of unimolecular rate theory is used to calculate the relative rates of the dissociation of a chemically activated ferrocene/ferrocenium precursor complex and the electron self-exchange process that produces the successor complex. Relative rates are used to calculate reaction efficiencies as a function of the estimated properties of the activated complexes for the two pathways. The RRKM model results are consistent with the high observed efficiency of the ferrocene reaction, but the results are sensitive to the assumed properties of the electron-transfer transition state. Particular attention is given to the effect of intermolecular degrees of freedom involving the interactions between the ferrocene and ferrocenium ion in the activated complex for electron transfer. These degrees of freedom must be modelled as either relatively unhindered internal rotations or low frequency vibrations (≲50 cm −1 ) to account for the observed reaction efficiency." @default.
- W2073219145 created "2016-06-24" @default.
- W2073219145 creator A5013414360 @default.
- W2073219145 creator A5028399374 @default.
- W2073219145 date "1993-10-01" @default.
- W2073219145 modified "2023-09-26" @default.
- W2073219145 title "Statistical rate theory of gas-phase electron transfer. The ferrocene/ferrocenium self-exchange reaction" @default.
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- W2073219145 doi "https://doi.org/10.1016/0301-0104(93)80254-7" @default.
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