TY - JOUR
T1 - Calculations of solid-state 43Ca NMR parameters
T2 - A comparison of periodic and cluster approaches and an evaluation of DFT functionals
AU - Holmes, Sean T.
AU - Bai, Shi
AU - Iuliucci, Robbie J.
AU - Mueller, Karl T.
AU - Dybowski, Cecil
N1 - Funding Information:
The authors acknowledge the Pennsylvania State University Center for Nanoscale Science for access to Accelrys? Materials Studio 7.0 and use of the Lionxv cluster. PNNL is operated for the U.S. DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.
Publisher Copyright:
© 2017 Wiley Periodicals, Inc.
PY - 2017/5/15
Y1 - 2017/5/15
N2 - We present a computational study of magnetic-shielding and quadrupolar-coupling tensors of 43Ca 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 predicting 43Ca 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 43Ca 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 43Ca chemical-shift tensors.
AB - We present a computational study of magnetic-shielding and quadrupolar-coupling tensors of 43Ca 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 predicting 43Ca 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 43Ca 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 43Ca chemical-shift tensors.
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U2 - 10.1002/jcc.24763
DO - 10.1002/jcc.24763
M3 - Article
C2 - 28233952
AN - SCOPUS:85013763617
VL - 38
SP - 949
EP - 956
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 13
ER -