The two high-spin Co(II) complexes, namely [Co(AcPyOx) 3 (BPh)] + and CoTp 2 , introduce significant first-order orbital contributions from the ground pseudodoublet orbital manifold within an almost trig- onal ligand field (see Table ). This leads to the emergence of four energetically lowest Kramers doublets (KDs) with SOC, as detailed in Table , expected to influence their temperature-dependent paramagnetic properties. Excited SF states minimally perturb the wavefunction composition and energy splitting of the KDs (see Tables and). The scorpionate complex CoTp 2 is one of the well studied molecules via magnetic resonance spectroscopic techniques to understand the ligand field effects of the trigonal symmetry. At least, the lowest four KDs were well identified experimentally as shown in Fig. which helps to compare the SO-CAS based results. The SO-CASPT2 g values of the individual KDs are in fair agreement with the experimental results, while the ligand field splitting is overestimated by more than 20%. The wavefunction analysis of the SO-CASPT2 ground KD indicates a contribution of almost 98% from the orbital doublet manifold while the immediate excited SF state at 2316 cm -1 (experimentally determined to be around 1900 cm -1 ) contributes by only ∼1.4%. Experimental magnetometry and paramagnetic NMR spectroscopy provide isotropic (χ) and anisotropic (∆ χ ax ) magnetic susceptibilities for the two Co(II) complexes, summarized in Table 1 . To compare the three approaches outlined in eqs. 10 to 9, the computed paramagnetic susceptibilities and their spin-only components ("s") are also provide in the Table . While the mPV and BB values only incorporate the contributions from the two lowest KDs (modeled with a S = 3/2) in an effective manner based on corresponding spin Hamiltonian (g and D) tensors, the VV approach directly includes the magnetic contributions from all the low lying KDs in a state-specific manner.