Electronic excitation and ionization spectra of cyclopentadiene (CP) were reinvestigated by the symmetry-adapted cluster (SAC) and SAC–configuration interaction (SAC-CI) method with an extended basis set and a wide active orbital space. To give a satisfactory interpretation of the general profile of the observed excitation spectrum, 40 low-lying excited singlet and triplet states (with excitation energies of up to 9.5 eV) were computed. The calculated excitation energies were greatly improved compared to those reported previously. All of the peaks in the experimental spectrum were reassigned theoretically with small deviations. The natures of the low-lying valence and Rydberg-excited states were discussed in detail, and the results were also compared with those of some other recent theoretical studies. The ionization energies calculated by the SAC-CI general-R method agree well with the experimental peaks in the photoelectron spectrum. A number of two-electron shake-up states were calculated below 23 eV.
Electronic excitation and ionization spectra of cyclopentadiene: Revisit by the symmetry-adapted cluster–configuration interaction method
Jian Wan, Masahiro Ehara, Masahiko Hada, Hiroshi Nakatsuji; Electronic excitation and ionization spectra of cyclopentadiene: Revisit by the symmetry-adapted cluster–configuration interaction method. J. Chem. Phys. 1 October 2000; 113 (13): 5245–5252. https://doi.org/10.1063/1.1290004
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