The Electronic Structures of CoGe n-/0 ( n = 1-3) Clusters from Multiconfigurational CASSCF/CASPT2 and RASSCF/RASPT2 Calculations.

Abstract

Density functional theory and multiconfigurational CASPT2 and RASPT2 methods are employed to investigate the low-lying states of CoGe n-/0 ( n = 1-3) clusters. With the RASPT2 approach, the active space is extended to 14 orbitals for CoGe-/0, 17 orbitals for CoGe2-/0, and 20 orbitals for CoGe3-/0. These active spaces include the 3d, 4s, and 4d of Co and 4p of Ge. The 4d of Co is incorporated into these active spaces in order to account for the important double-shell effect of Co. The structural parameters, vibrational frequencies, and relative energies of the low-lying states of CoGe n-/0 ( n = 1-3) are reported. The ground states of CoGe n- ( n = 1-3) are computed to be 3Φ of linear CoGe-, 3B1 of cyclic CoGe2-, and 3B1 of cyclic CoGe3- isomer. The ground states of the neutral clusters are calculated to be 2Δ of linear CoGe, 4B1 of cyclic CoGe2, and 4A″ of tetrahedral CoGe3 isomer. The calculated adiabatic and vertical detachment energies of the anionic ground states are in agreement with the experimental values as observed in the 266 nm anion photoelectron spectra.