Conformational dependence of electronic spectra in the nitroxide series: a MCSCF/CI study

We report a systematic study of the relation between the electronic spectra of nitroxide free radicals and their deviation from planarity, taking H2NO as a model compound. Using a MCSCF/CI treatment specifically designed to account for the characteristics of the nitroxide group, we have shown that the bathochromic shift of the n-π∗ electronic transition is a sensitive signature of the geometry of these radicals.