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Calculations of solid‐state 43 Ca NMR parameters: A comparison of periodic and cluster approaches and an evaluation of DFT functionals
Author(s) -
Holmes Sean T.,
Bai Shi,
Iuliucci Robbie J.,
Mueller Karl T.,
Dybowski Cecil
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24763
Subject(s) - coupled cluster , cluster (spacecraft) , chemical shift , chemistry , density functional theory , electromagnetic shielding , solid state , computational chemistry , molecule , physics , quantum mechanics , computer science , organic chemistry , programming language
We present a computational study of magnetic‐shielding and quadrupolar‐coupling tensors of 43 Ca 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 43 Ca 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 43 Ca 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 43 Ca chemical‐shift tensors. © 2017 Wiley Periodicals, Inc.