Evaluation of Approximate Exchange-Correlation Functionals in Predicting One-Bond 31P-1H NMR Indirect Spin-Spin Coupling Constants

This work benchmarks density functional theory, with several different exchange-correlation functionals, for prediction of isotropic one-bond phosphorus-hydrogen NMR spin-spin coupling constants (SSCCs). Our test set consists of experimental SSCCs from 30 diverse molecules representing multiple phosphorus bonding environments. The results suggest the importance of a balance between the choice of correlation functional and the admixture of nonlocal exchange. Overall, standard DFT methods appear to suffice for usefully accurate predictions of P-31-H-1 SSCCs.