Interpretation of photoelectron spectra of CoGe_n^- (n = 4, 5) clusters by multiconfigurational RASPT2 calculations

The low-lying electronic states CoGe_n^-/0 (n = 4, 5) have been investigated with density functional theory and the state-of-the-art RASSCF/RASPT2 method to give assignments for the anion photoelectron spectra. The BP86 functional was employed to optimize the geometrical structures of the electronic states, while the RASSCF/RASPT2 was applied to calculate the single-point energies. With the RASSCF/RASPT2 approach, the active spaces are extended to a size of 21 orbitals for CoGe₄^-/0 and 24 orbitals for CoGe₅^-/0. The ground states of CoGe₄^-/0 are determined to be ³A″ and ²A″ of a trigonal bipyramidal structure in which the Co atom is situated at the equatorial corner of the bipyramid. The vertical detachment energies of the transitions from the anionic ground state to the neutral ²A″, 1⁴A″, ²A', 2⁴A″, 3⁴A″, 1⁴A', 2⁴A', and 6⁴A″ states are evaluated to be 2.29, 2.39, 2.60, 2.83, 3.17, 3.24, 3.47, and 4.00 eV. For the CoGe₅^-/0 clusters, the ground states are computed to be ¹A₁ and 1²A₂ of an octahedral structure. The vertical detachment energies of the removal of one electron from the anionic ground state to result in the 1²A₂, 1²A₁, 2²A₁, 1²B₁, 1²B₂, 4²B₁, 4²B₂, and 6²A₂ states are estimated to be 2.16, 2.79, 2.84, 3.06, 3.06, 3.59, 3.59, and 4.22 eV. All features in the photoelectron spectra of CoGe₄^- and CoGe₅^- are interpreted based on the computed electron detachment energies of the anionic ground states.