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Issue 12, 1994
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Molecular orbital studies of electron-transfer reactions


Our previous AM1 semiempirical molecular orbital studies on the electron self-exchange reaction between p-diaminobenzene (PPD) and its radical cation have been extended to include dynamics calculations of the inner-sphere vibrational frequency, νi, and a configuration interaction (Cl) study of the distance dependence of the transfer-integral, V12. These and our previous results for the reorganization energy, λ, and the classical activation barrier to electron transfer have been used to calculate a unimolecular gas-phase rate constant, Ket, of (3–7)× 1010 s–1, compared with an experimental value in acetonitrile of 2 × 108 s–1. The solvent is thus suggested to lower Ket by a factor of 150–3350 for this reaction.

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Article information

J. Chem. Soc., Faraday Trans., 1994,90, 1783-1788
Article type

Molecular orbital studies of electron-transfer reactions

G. Rauhut and T. Clark, J. Chem. Soc., Faraday Trans., 1994, 90, 1783
DOI: 10.1039/FT9949001783

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