NMR chemical shielding for solid-state systems using spin-orbit coupled ZORA GIPAW.

Area of Science:

• Computational chemistry
• Quantum chemistry
• Solid-state physics

Background:

• Nuclear magnetic resonance (NMR) spectroscopy is crucial for characterizing materials.
• Accurate computation of NMR chemical shielding tensors requires accounting for relativistic effects, especially for heavy elements.
• Spin-orbit coupling (SOC) significantly influences electronic structure and NMR properties in heavy elements.

Purpose of the Study:

• To implement and validate a computational method for calculating NMR chemical shielding tensors including spin-orbit coupling (SOC) in solid-state systems.
• To address the challenges of incorporating SOC within the projector augmented waves (PAW) framework for periodic systems.
• To assess the accuracy of the developed method by comparing results with existing approaches.

Main Methods:

• Implementation of SOC within linear response theory using the Vienna Ab initio Simulation Package (VASP).
• Application of periodic boundary conditions and the gauge-including projector augmented waves (PAW) approach.
• Inclusion of relativistic effects using the zeroth-order regular approximation (ZORA).

Main Results:

• The developed method shows good agreement with established local-basis ZORA implementations.
• Successful application to molecules and cluster approximations of crystalline systems containing Sn, Hg, and Pb.
• Demonstrated capability to handle challenges associated with PAW basis sets for SOC calculations.

Conclusions:

• The presented implementation provides a reliable tool for computing NMR chemical shielding tensors with SOC in solid-state systems.
• The method accurately captures relativistic effects crucial for heavy elements.
• This work advances the computational study of NMR properties in materials containing heavy atoms.