where σ orb Ki j is the component of the orbital chemical shielding tensor usually evaluated from the DFT based methods following a Ramsey-type development . The temperature dependent second term is known as the paramagnetic chemical shielding tensor σ p Ki j where χ s ik is the component of the spin-only molar magnetic susceptibility tensor and the A Kk j is the component of the probing metalnuclear hyperfine tensor, γ K is the gyromagnetic ratio of the nucleus, ℏ is the reduced Plank constant, g e is the free-electron g-factor, µ 0 is the magnetic permeability, µ B is the Bohr magneton, and N A is the Avogadro number. The χ s tensor is evaluated directly from the first principles multiconfigurational spin-orbit complete active space (SO-CAS) according to a Van Vleck type model equation (eq. 9), hence called VV approach here. The VV approach equation (eq. 1) is the presentation of the general equa-tion (eq. 8) previously formulated by Soncini and Van den Heuvel in terms of magnetic susceptibility where one time occurrence of the magnetic moment is included by computing only the spin-only component to the magnetic susceptibility, while in the Van Vleck susceptibility the occurrence of the magnetic moment is twice. Following a sum-over-states evaluation of the shielding tensor according to eq. 8 either within a DFT framework or directly from a multiconfigurational space was implemented previously by Autschbach et al. ]. An effective first principles evaluation of both the χ s and A tensors in eq. 1 from the same Hilbert space provides an alternate route to solve eq. 8 within a large space. Eq. 1 reduces to the earlier model equations based on spin Hamiltonian parameters developed (and later modified) by Pennanen and Vaara (mPV approach) and Bleaney (BB approach) when one evaluates χ s tensor according to eq. 10 and zero field contribution in eq. 10 with eq. 11, respectively. The QC evaluation of the A K tensor from a Hilbert space of multiconfigurational character is nontrivial, mainly due to the Fermi-contact contribution. So mostly in the literature the A K tensors in the transition metal complex are evaluated using unrestricted DFT-based methods based on an orbital-level perturbation treatment of the spin-orbit coupling (SOC). A hybrid approach is also benchmarked here for the considered transition metal complexes where the dipolar components of the hyperfine tensors are evaluated from the SO-CAS methods based on an effective spin and the Fermicontact contributions are from the unrestricted DFT methods.