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Keywords:

  • ab initio calculations;
  • bicyclohexylidenes;
  • olefins;
  • Rydberg–valence mixing;
  • UV/Vis spectroscopy

Abstract

The electronic excited states of the olefin 1,1′-bicylohexylidene (BCH) are investigated using multiconfigurational complete active space self-consistent-field second order perturbation theory in its multi-state version (MS-CASPT2). Our calculations undoubtedly show that the bulk of the intensity of the two unusually intense bands of the UV absorption of BCH measured with maxima at 5.95 eV and 6.82 eV in the vapor phase are due to a single ππ* valence excitation. Sharp peaks reported in the vicinity of the low-energy feature in the gas phase correspond to the beginning of the π3sR Rydberg series. By locating the origin of the ππ* band at 5.63 eV, the intensity and broadening of the observed bands and their presence in solid phase is explained as the vibrational structure of the valence ππ* transition, which underlies the Rydberg manifold as a quasi-continuum.