title: Calculations of solid-state43Ca NMR parameters: A comparison of periodic and cluster approaches and an evaluation of DFT functionals.
abstract: We present a computational study of magnetic-shielding and quadrupolar-coupling tensors of43Ca sites in crystalline solids. A comparison between periodic and cluster-based approaches for modeling solid-state interactions demonstrates that cluster-based approaches are suitable for predicting43Ca 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 of43Ca 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 of43Ca chemical-shift tensors. © 2017 Wiley Periodicals, Inc.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
authors.forename: Sean T
authors.initials: ST
authors.lastname: Holmes
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
authors.forename: Shi
authors.initials: S
authors.lastname: Bai
authors.affiliation: Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania, 15301.
authors.forename: Robbie J
authors.initials: RJ
authors.lastname: Iuliucci
authors.affiliation: Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania, 16802.|Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington, 99352.
authors.forename: Karl T
authors.initials: KT
authors.lastname: Mueller
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, 19716.
authors.forename: Cecil
authors.initials: C
authors.lastname: Dybowski
keywords: NMR; calcium; density-functional theory; gauge-including-projector-augmented-wave