Journal of Chemical Physics, Vol.111, No.23, 10550-10554, 1999
Calculations on the Jahn-Teller configurations of the benzene cation
The analysis of the zero-electron-kinetic-energy photoelectron spectra of benzene has led to a reinvestigation by ab initio methods of the electronic states of the C6H6+ cation resulting from Jahn-Teller distortions on ionization. The calculations involving a range of currently used methodologies all verify that the two cation configurations, B-2(2g) and B-2(3g) of D-2h symmetry, resulting from removal of an electron from the e(1g)(pi) degenerate MOs of C6H6, comprise a true minimum and a transition state, differing only slightly in energy. These are linked through the in-plane b(1g) vibration, confirming that b(1g) is actually a pseudorotational coordinate. Hence C6H6+ exhibits similar structural floppiness to the cations of methane and cyclopropane although with a much smaller barrier to pseudorotation than for these smaller species. These results support the general proposition that such Jahn-Teller distortions associated with molecular ionization (of stable closed-shell hydrocarbon molecules of high symmetry) generally involve a quadratic contribution which leads to a single global minimum cation structure, with all other derived stationary states being transition states each characterized by a single imaginary vibration frequency.