Semi-occupied molecular orbitals SOMOs

The strong electronic absorption of alkane radical cations is readily understood in molecular orbital terms. Extending down from the highest occupied molecular orbital (HOMO) is a rather closely packed set of valence molecular orbitals, that are clearly displayed in the photoelectron spectra (PES) of neutral alkanes. The electronic absorption of alkane radical cations is due to transitions (induced by photon absorption) of electrons from such lower-lying molecular orbitals to the semi-occupied molecular orbital (SOMO), which is the highest-occupied molecular orbital in the ground-state ion. By illumination within the (broad and largely unstructured) absorption band of alkane radical cations, electronically excited states of alkane radical cations can thus be created in a quite convenient way. 

Spin densities (p) are theoretical quantities, defined as the sum of the squared atomic orbital coefficients in the nonbonding semi-occupied molecular orbital (SOMO) of the radical species (Hiickel theory). For monoradical species, the spin density is connected to the experimental EPR hyperfine coupling constant a through the McConnell equation [38]. This relation provides the opportunity to test the spin density dependence of the D parameter [Eq. (8)] for the cyclopentane-1,3-diyl triplet diradicals 10 by comparing them with the known experimental hyperfine coupling constants (ap) of the corresponding substituted cumyl radicals 14 [39]. The good semiquadratic correlation (Fig. 9) between these two EPR spectral quantities demonstrates unequivocally that the localized triplet 1,3-diradicals 9-11 constitute an excellent model system to assess electronic substituent effects on the spin density in cumyl-type monoradicals. 

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