Relocalization isomers are configurational isomers connected by a vibronic pathway that redistributes electron density, altering orbital hybridizations and molecular geometry without changing the sequence of chemical bonds. We report a computational study of the most stable acroleinyl free radicals, which exhibit potential energy surfaces (PES) with distinct, non-equivalent minima, separated by small energy barriers. A three-dimensional potential energy surface has been calculated at the explicitly correlated coupled cluster level. Unlike the HC3O radical, which we have studied previously, the distinct minima on the acroleinyl surface do not share a common electronic state symmetry, and the configurational isomerization involves a straightforward symmetry breaking.  The vibrational eigenvalues and eigenvectors are solved on this surface using the finite element method, and used to predict rovibrational energies and effects of vibrational averaging that may help identify and quantify effects of the isomerization on infrared spectra.

Vibrational energy levels of acrolein related free radicals as determined by a finite element approach

243rd National Meeting (2012)

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