Benchmark accuracy of predicted NMR observables for quadrupolar ¹⁴ N and ¹⁷ O nuclei in molecular crystals

Nuclear quadrupole resonances for $$ and ¹⁷ O nuclei are exquisitely sensitive to interactions with surrounding atoms. As a result, nitrogen and oxygen solid-state nuclear magnetic resonance (ssNMR) provides a powerful tool for investigating structure and dynamics in complex systems. First-principles calculations are increasingly used to facilitate spectral assignment and to evaluate and adjust crystal structures. Recent work combining the strengths of planewave density functional theory (DFT) calculations with a single molecule correction obtained using a higher level of theory has proven successful in improving the accuracy of predicted chemical shielding (CS) tensors and ¹⁷ O quadrupolar coupling constants ( $$ ). Here we extend this work by examining the accuracy of predicted ¹⁴ N and ¹⁷ O electric field gradient (EFG) tensor components obtained using alternative planewave-corrections involving cluster and two-body fragment-based calculations. We benchmark the accuracy of CS and EFG tensor predictions for both nitrogen and oxygen using planewave, two-body fragment, and enhanced planewave-corrected techniques. Combining planewave and two-body fragment calculations reduces the error in predicted ¹⁷ O $$ values by 35% relative to traditional planewave calculations. These enhanced planewave-correction methods improve the accuracy of ¹⁷ O and ¹⁴ N EFG tensor components by 15% relative to planewave DFT but yield minimal improvement relative to a simple molecular correction. However, in structural environments involving either high symmetry or strong intermolecular interactions, enhanced planewave-corrected methods provide a distinct advantage.