Dynamical jahn-teller effect in hydrocarbon radicals

Abstract

The first part of this paper shows how the ordinary Born-Oppenheimer approximation for separating nuclear and electronic motion can be adapted to a degenerate electronic state. To set up equations of motion for the dynamical Jahn-Teller effect in their simplest form we use vibrational amplitudes associated with special linear combinations of the degenerate electronic wave functions, chosen to vary as slowly as possible with nuclear displacements. We also discuss briefly the symmetry-forbidden electronic transitions allowed by a Jahn-Teller distortion. In the second we make molecular orbital calculations of the energies and distorted shapes of some aromatic hydrocarbon molecules. The differences in energy between the distorted and symmetrical shapes (inkcal/mole) are cyclobutadiene 11.43; cyclopentadienyl 1.414, cycloheptatrienyl 0.859; benzene negative ion 1.077; triphenylene and coronene negative ions 0.385 and 0.299. In the last three each shape of minimum energy is separated from two equivalent ones by a small potential barrier, respectively, 0.000,0.001, and 0.002, The ground state of each radical is doubly degenerate, and it can oscillate about a continuous series of distorted shapes. In the excited 1E1u+ and 3E1u+ states of benzene the distortions are much smaller, and the CC bonds probably bend rather than stretch.