Treatment of the Multimode Jahn–Teller Problem in Small Aromatic Radicals

Abstract

The family of the Jahn-Teller (JT) active hydrocarbon rings, C(n)H(n) (n = 5-7), was analyzed by the means of multideterminantal density functional theory (DFT) approach. The multimode problem was addressed using the intrinsic distortion path (IDP) method, in which the JT distortion is expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Partitioning of the stabilization energy into the various physically meaningful terms arising from Kohn-Sham DFT has been performed to get further chemical insight into the coupling of the nuclear movements and the electron distribution.