A valence bond analysis of electronic degeneracies in Jahn-Teller systems: low-lying states of the cyclopentadienyl radical and cation.
The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D(5h) structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.
Department of Physical Chemistry, Farkas Center for Light-Induced Reactions, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Shmuel
S
Zilberg
Yehuda
Y
Haas