Electron Detachments of NbSi^-/0 (n = 1-3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations

The electronic states of NbSi^-/0/+ (n = 1-3) clusters have been explored using the state-of-the-art DMRG-CASPT2 method with relatively large active spaces. The leading configurations, bond distances, vibrational frequencies, and relative energies of the low-lying states were identified. Electron detachment energies of the anionic cluster and ionization energies of the neutral clusters were reported at the DMRG-CASPT2 level. The ground states of the NbSi^-/0/+ (n = 1-3) clusters were predicted as the ³Δ, ⁴Π, and ⁵Π states of the linear NbSi^-/0/+, the ³A₂, ⁴B₁, and ³B₁ states of cyclic NbSi₂^-/0/+, and the ¹A', ²A', and ³A″ states of tetrahedral NbSi₃^-/0/+ isomers. The first feature in the photoelectron spectrum of NbSi^- was attributed to the transitions from the anionic ³Δ ground state to the neutral ⁴Π, ⁴Δ, and ⁴Φ states, whereas the second feature was assigned to the transitions to the neutral ²Δ, ²Σ⁺, and ²Φ states. The first band in the photoelectron spectrum of NbSi₃^- was ascribed to the transition from the anionic ¹A' ground state to the neutral 1²A' and 1²A″ states; the second band was attributed to the transitions to 2²A', 2²A″, and 3²A' states; and the third band was assigned to the transition to 3²A' states.