Quantitative calculation of magnetic and electric properties in a d(2)–d(3) mixed-valence vanadium dimer complex.

The electronic structure and magnetic properties in the mixed-valence d(2)-d(3) vanadium dimer complex ((PY5Me(2))(2)V(2)(μ-5, 6-dmbzim))(4+) under an electric field are investigated by using the density functional theory and the effective Hamiltonian method. With the aim of controlling the localization-delocalization of the excess electron, an electric field is applied in the direction along the two vanadium atoms. The ground state changes with an increase of the electric field from the highest spin S D 5=2 state to the intermediate spin S D 3=2 state, and then it changes to the lowest spin S D 1=2 state. Thus, in this realistic mixed-valence dimer system, the possibility of controlling the spin state by using the electric field is shown. Various magnetic and electric properties of this mixed-valence dimer complex are also calculated using our effective Hamiltonian. The methodology in this paper is quite general and is a useful approach for the calculation of electronic structures in various magnetic complexes.