Theoretical study on the anion photoelectron spectra of Ln(COT)2− including the spin-orbit effects

Abstract

The multiplet level splittings for both anion and neutral sandwich complexes Ln(COT)2 (Ln=Ce-Yb, COT=1,3,5,7-cyclooctatetraene) were calculated with spin-orbit interactions to analyze their anion photoelectron spectra. The theoretically simulated spectra obtained with these energies and the pole strengths are generally consistent with the experimental spectra for the X peak. The magnitudes of the energy splittings, relative peak intensities, and their Ln dependence are reproduced. In comparison to our previous calculations, the inclusion of spin-orbit interactions with the SO-MCQDPT2 method makes the simulated spectra more consistent with the results of the experiment.