Electronic States of CoSin-/0/+ (n = 1-3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations.

Density matrix renormalization group-CASPT2 (DMRG-CASPT2), CASPT2, and density functional theory are employed to describe the complicated geometrical and electronic structures of CoSin-/0/+ (n = 1-3) clusters. The active spaces of DMRG-CASPT2 are extended to 23 orbitals. The DMRG-CASPT2 method with such large active spaces is reasonable to provide highly accurate relative energies of the electronic states. The pure BP86, PBE, and TPSS functionals appear to be suitable to compute the relative energies of the electronic states of cobalt-doped silicon clusters. The leading configurations, bond distances, vibrational frequencies, normal modes, and relative energies of the electronic states are reported. The electron detachment energies of the removals of one electron from the anionic and neutral clusters are estimated. All six bands in the photoelectron spectrum of CoSi3- are interpreted based on the computed electron detachment energies and Franck-Condon factor simulations.