Magnetostructural Dependencies in $3d^2$ Systems: The Trigonal Bipyramidal V$^{3+}$ Complex

Abstract: We introduce a multi-configurational approach to study the magneto-structural correlations in $3d^2$ systems. The theoretical framework represents a restricted active space self-consistent field method, with active space optimized to the number of all non-bonding orbitals. To demonstrate the validity and effectiveness of the method, we explore the physical properties of the trigonal bipyramidal spin-one single-ion magnet (C$_6$F$_5$)$_3$trenVCN$^t$Bu. The obtained theoretical results show a good agreement with the experimental data available in the literature. This includes measurements for the magnetization, low-field susceptibility, cw-EPR and photoluminescence spectroscopy. The proposed method may be reliably applied to a variety of $3d^2$ magnetic systems. To this end, and for the sake completeness, we provide detailed analytical and numerical representations for the generic Hamiltonian's effective matrix elements related to the crystal field, exchange, spin-orbit and Zeeman interactions.