Abstract
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.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 949-956 |
| Number of pages | 8 |
| Journal | Journal of Computational Chemistry |
| Volume | 38 |
| Issue number | 13 |
| DOIs | |
| State | Published - May 15 2017 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
- Computational Mathematics
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Calculations of solid-state 43Ca NMR parameters : A comparison of periodic and cluster approaches and an evaluation of DFT functionals. / Holmes, Sean T.; Bai, Shi; Iuliucci, Robbie J.; Mueller, Karl Todd; Dybowski, Cecil.
In: Journal of Computational Chemistry, Vol. 38, No. 13, 15.05.2017, p. 949-956.Research output: Contribution to journal › Article
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 Todd
AU - Dybowski, Cecil
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.
UR - http://www.scopus.com/inward/record.url?scp=85013763617&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85013763617&partnerID=8YFLogxK
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 -