Density functional theory investigation of 3d transition metal NMR shielding tensors in diamagnetic systems using the gauge-including projector augmented-wave method

We present a density functional theory based method for calculating NMR shielding tensors for 3d transition metal nuclei using periodic boundary conditions. Calculations employ the gauge-including projector augmented-wave pseudopotential method. The effects of ultrasoft pseudopotential and induced approximations on the second-order magnetic response are intensively examined. The reliability and the strength of the approach for ⁴⁹Ti and ⁵¹V nuclei are shown by comparison with traditional quantum chemical methods using benchmarks of finite organometallic systems. Application to infinite systems is validated through comparison to experimental data for the ⁵¹V nucleus in various vanadium oxide based compounds. The successful agreement obtained for isotropic chemical shifts contrasts with full estimation of the shielding tensor eigenvalues, revealing the limitation of pure exchange-correlation functionals compared to their exact-exchange corrected analogs.