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Optica Publishing Group
  • Applied Spectroscopy
  • Vol. 47,
  • Issue 12,
  • pp. 2140-2144
  • (1993)

On the Correlation Between Electronic Spectra of Alternant Aromatic Hydrocarbons and Their Radical Cations

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Abstract

On the basis of the spectroscopic data for some 40 alternant aromatic hydrocarbons, a simple correlation is given between the excited singlet state (<i>p</i> band) of such molecules and the excited lowest-energy non-Koopmans state (<i>A</i> band) for their radical cations. It is shown that, with the use of this relation, the energy of the doublet state for a radical cation can be reasonably estimated if the energy of the <i>p</i> band for its neutral precursor is known. We have also computed the doublet state energies of the aromatic hydrocarbons using the "SDT" relations, which involve three spectroscopic quantities, <i>viz</i>., the excited singlet (<i>S</i>) and triplet (<i>T</i>) states of a neutral molecule and the doublet (<i>D</i>) state of its radical cation. The predictions of the proposed singlet-doublet state correlation are found to be far superior than those of the SDT relations.

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