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

TL;DR

This paper introduces a DFT-based method using the gauge-including projector augmented-wave approach to calculate NMR shielding tensors for 3d transition metals in periodic systems, validated against experimental and quantum chemical data.

Contribution

It develops and validates a novel computational approach for NMR shielding tensors in transition metals within periodic boundary conditions, addressing limitations of previous methods.

Findings

Accurate NMR shielding tensors for 49Ti and 51V nuclei demonstrated.

Method shows good agreement with experimental data for vanadium oxides.

Limitations identified in exchange-correlation functionals for eigenvalue estimation.

Abstract

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 pseudopotentials 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 is 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 analogues.