Multiconfigurational CASSCF/CASPT2 method is carried out to investigate the geometrical and electronic structures of diatomic VSi0/−/+ clusters. The potential energy profiles of the electronic states are built based on the CASPT2 single‐point energies. From the potential energy profiles, the bond distances, vibrational frequencies, and relative energies of the electronic states are determined. The ionization energy and electron affinity of the neutral cluster are calculated. All the results presented in this work are important to explain the spectroscopic data of VSi0/−/+ clusters

The low‐lying states of TaGe−/0/+ clusters have been investigated with the CASPT2 and DMRG‐CASPT2 methods. The DMRG‐CASPT2 method with an active space of 20 orbitals is expected to provide highly accurate relative energies of the electronic states. The leading configurations, bond distances, bond orders, vibrational frequencies, atomic charges, and relative energies of the electronic states are reported. The ground states of TaGe−/0/+ clusters are respectively predicted as the 3Δ, 4Φ, and 5Δ. The atomic charges of Ta in these ground states are more positive than those of the Ge atom. The electron detachment energies of the anionic and neutral clusters are estimated to be 1.62 and 6.84 eV. The Franck‐Condon factor simulations for the detachments of one electron from the anionic and neutral clusters exhibit extensively vibrational progressions because of the large structural difference between the initial and the final state.