Calculations of Solid-State 43Ca NMR Parameters: A Comparison of Periodic and Cluster Approaches and an Evaluation of DFT Functionals

We present a computational study of magnetic-shielding and quadrupolar-coupling tensors of Ca-43 sites in crystalline solids. A comparison between periodic and cluster-based approaches for modeling solid-state interactions demonstrates that clusterbased approaches are suitable for predicting Ca-43 NMR parameters. Several model chemistries, including Hartree-Fock theory and 17 DFT approximations (SVWN, CA-PZ, PBE, PBE0, PW91, B3PW91, rPBE, PBEsol, WC, PKZB, BMK, M06-L, M06, M06-2X, M06-HF, TPSS, and TPSSh), are evaluated for the prediction of Ca-43 NMR parameters. Convergence of NMR parameters with respect to basis sets of the form cc-pVXZ (X-D, T, Q) is also evaluated. All DFT methods lead to substantial, and frequently systematic, overestimations of experimental chemical shifts. Hartree-Fock calculations outperform all DFT methods for the prediction of Ca-43 chemical-shift tensors. (C) 2017 Wiley Periodicals, Inc.