Modeling of the mechanism of one-electron transfer from the perylene molecule to the oxygen molecule 3O2 in the HF medium

Abstract

The thermodynamic parameters of the formation of the perylene radical cation in anhydrous hydrogen fluoride containing dissolved dioxygen were calculated by the ab initio method MP2. The protonated product of HF autoprotolysis was modeled as the H(FH) +3 cluster. The 3O2 molecule was found to bind to the linear H(FH) +3 cluster via a hydrogen bond. As the charge and multiplicity of the system change upon the capture of an electron, the oxygen-hydrogen fluoride cluster complex undergoes rearrangement to yield the hydroperoxyl radical OOH incorporated in a cycle formed by HF molecules. The free energy of electron transfer from the perylene molecule to the 3O2 molecule in the HF medium is about −38 kcal/mol.

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Correspondence to V. N. Solkan.

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Original Russian Text © I.V. Kuz’min, V.N. Solkan, G.M. Zhidomirov, V.B. Kazanskii, 2011, published in Kinetika i Kataliz, 2011, Vol. 52, No. 2, pp. 199–203.

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Kuz’min, I.V., Solkan, V.N., Zhidomirov, G.M. et al. Modeling of the mechanism of one-electron transfer from the perylene molecule to the oxygen molecule 3O2 in the HF medium. Kinet Catal 52, 192 (2011). https://doi.org/10.1134/S002315841102011X

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Keywords

  • Radical Cation
  • Butadiene
  • Dioxygen
  • Perylene
  • Hydrogen Fluoride