The ionic states of cyclooctatetraene: Analysis of a new experimental photoelectron spectrum by ab initio and density functional methods

A synchrotron-based study of the photoelectron spectrum (PES) for cyclooctatetraene (COT) is reported, and this has been subjected to theoretical analysis in unprecedented detail. Weak vibrational structure was observed on the lowest ionization energy (IE1), but the peaks generally show very broad features. Multiconfiguration self-consistent field study confirms that the adiabatic IE (AIE) sequence is 1(2)A(1) < 1(2)B(1) < 2(2)A(1) < 1(2)A(2) < 2(2)B(1) < 3(2)A(1). The Tamm-Dancoff approximation gives an acceptable interpretation of the PES below 20 eV. Vibrational analysis of the PES bands by Franck-Condon methods predicts well-defined vibrational structure for these ionic states. The principal contributors to the PES envelopes are the a1 modes, and only a few are responsible for the overall shape of most bands. The high density of vibrational states, together with the known D-2d reversible arrow D-2d interconversion process, where the C=C and C-C bonds interchange, is attributed to the lack of the observed structure. The transition state (TS) structures for the interconversion above of several ionic states of COT have been elucidated. The intrinsic reaction coordinate procedure gave a planar TS for the X(1)A(1) (D-2d) reversible arrow (1)A(1g) (D-4h) reversible arrow X(1)A(1) (D-2d) process; this shows alternating C-C (1.4791 angstrom), C=C (1.3261 angstrom), and C-H (1.0780 angstrom) bond lengths. The planar TS is a very shallow maximum, with energy varying with the method used, Hartree-Fock 0.575 eV and second order Moller-Plesset 0.653 eV. A polynomial containing quadratic, quartic, and sextic terms gives an effectively exact fit to the surface. The lowest ionic state of COT (X2A1) shows a similar TS for the process X(2)A(1) (D-2d) reversible arrow B-2(2u) (D-4h). This structure has alternating C-C (1.4366 angstrom), C=C (1.3572 angstrom), and C-H (1.0756 angstrom) bonds. Published under license by AIP Publishing.