Electronic excitation spectra of furan and pyrrole: Revisited by the symmetry adapted cluster–configuration interaction method

Abstract

Electronic excitation spectra of furan and pyrrole are reinvestigated by the symmetry-adapted cluster configuration-interaction method. The 47 and 46 lowest singlet and triplet electronic states are computed for furan and pyrrole, respectively. Two series (1a2 and 2b1) of low-lying Rydberg states and the valence π–π* excited states strongly influence each other in both furan and pyrrole. The present calculations give detailed and satisfactory theoretical assignments of the vacuum ultraviolet spectra and the electron energy-loss spectra of the two molecules. The similarities and differences in the electronic excitations between furan and pyrrole are discussed in detail. The accuracy and assignments of recent theoretical studies, i.e., complete active space second-order perturbation, multireference Møller–Plesset perturbation, second-order algebraic-diagrammatic construction, multireference double configuration interaction, and CC3, are compared.