PHOTODETACHMENT OF ELECTRONS FROM ANIONS OF HIGH SYMMETRY - ELECTRON PHOTODETACHMENT SPECTRA OF THE CYCLOOCTATETRAENYL AND PERINAPHTHENYL ANIONS

The reported experimental photodetachment cross sections for the cyclooctatetraenyl radical anion 1 and the perinaphthenyl anion 2 provide the first examples of detachment from molecular orbitals of very high angular momentum, and theoretical aspects of the electron photodetachment of highly symmetric molecules are discussed. Partially orthogonalized plane wave (POPW) theory is used to estimate the vertical electron detachment energy of cyclooctatetraenyl anion at about 1 eV and the adiabatic electron affinity of the perinaphthenyl radical at 1.07 ±0.1 eV. Resonances in the photodetachment cross section at 330 nm for 1 and at 420 and 530 nm for 2 are assigned to autodetaching π to π* excited states of the respective anions. © 1979, American Chemical Society. All rights reserved.