NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations

TL;DR

This paper benchmarks the GIPAW method against all-electron calculations for NMR shieldings, showing excellent agreement and highlighting significant relativistic effects in deshielded nuclei.

Contribution

It provides a comprehensive comparison of GIPAW with all-electron methods for NMR shieldings, emphasizing the importance of relativistic effects.

Findings

GIPAW results agree well with all-electron calculations

Relativistic effects are significant for deshielded nuclei

Small component contributions are substantial in relativistic corrections

Abstract

We present a benchmark of the density functional linear response calculation of NMR shieldings within the Gauge-Including Projector-Augmented-Wave method against all-electron Augmented-Plane-Wave$+$local-orbital and uncontracted Gaussian basis set results for NMR shieldings in molecular and solid state systems. In general, excellent agreement between the aforementioned methods is obtained. Scalar relativistic effects are shown to be quite large for nuclei in molecules in the deshielded limit. The small component makes up a substantial part of the relativistic corrections.