A Quest for Effective ¹⁹F NMR Spectra Modeling: What Brings a Good Balance Between Accuracy and Computational Cost in...

This work proposes a systematic study of different computational schemes for fluorine Nuclear Magnetic Resonance (¹⁹F NMR) chemical shifts, with special emphasis placed on the basis set issue. This study encompasses two stages of calculation, namely, the development of the computational schemes for the geometry optimization of fluorine compounds and the NMR chemical shift calculations. In both stages, the performance of different density functional theory functionals is considered against the method of coupled-cluster singles and doubles (CCSD), with the latter representing a theoretical reference in this work. This exchange-correlation functional study is accompanied with a basis set study in both stages of calculation. Basis sets of different families, sizes, and valence-splitting levels are considered. Various locally dense basis sets (LDBSs) are proposed for the calculation of ¹⁹F NMR chemical shifts, and their performance is assessed by comparison of the calculated chemical shifts with both theoretical and experimental reference data. Overall, the pcS-3/pcS-2 LDBS scheme is recommended as the most balanced locally dense basis set scheme for fluorine chemical shift calculations.