Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

Abstract

Density functional theory (DFT) was used to estimate water's isotropic nuclear shieldings and indirect nuclear spin-spin coupling constants (SSCCs) in the Kohn-Sham (KS) complete basis set (CBS) limit. Correlation-consistent cc-pVxZ and cc-pCVxZ (x = D, T, Q, 5, and 6), and their modified versions (ccJ-pVxZ, unc-ccJ-pVxZ, and aug-cc-pVTZ-J) and polarization-consistent pc-n and pcJ-n (n = 0, 1, 2, 3, and 4) basis sets were used, and the results fitted with a simple mathematical formula. The performance of over 20 studied density functionals was assessed from comparison with the experiment. The agreement between the CBS DFT-predicted isotropic shieldings, spin-spin values, and the experimental values was good and similar for the modified correlation-consistent and polarization-consistent basis sets. The BHandH method predicted the most accurate (1)H, (17)O isotropic shieldings and (1)J(OH) coupling constant (deviations from experiment of about -0.2 and -1 ppm and 0.6 Hz, respectively). The performance of BHandH for predicting water isotropic shieldings and (1)J(OH) is similar to the more advanced methods, second-order polarization propagator approximation (SOPPA) and SOPPA(CCSD), in the basis set limit.