Calculations of solid-state 43Ca NMR parameters: A comparison of periodic and cluster approaches and an evaluation of DFT functionals

Sean T. Holmes, Shi Bai, Robbie J. Iuliucci, Karl Todd Mueller, Cecil Dybowski

Research output: Contribution to journalArticle

8 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)949-956
Number of pages8
JournalJournal of Computational Chemistry
Volume38
Issue number13
DOIs
StatePublished - May 15 2017

Fingerprint

Discrete Fourier transforms
Nuclear magnetic resonance
Chemical shift
Tensors
Evaluation
Tensor
Magnetic shielding
Solid Modeling
Prediction
Chemistry
Crystalline materials
Approximation
Interaction
Demonstrate
Model
Form

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Computational Mathematics

Cite this

Holmes, Sean T. ; Bai, Shi ; Iuliucci, Robbie J. ; Mueller, Karl Todd ; Dybowski, Cecil. / Calculations of solid-state 43Ca NMR parameters : A comparison of periodic and cluster approaches and an evaluation of DFT functionals. In: Journal of Computational Chemistry. 2017 ; Vol. 38, No. 13. pp. 949-956.
@article{f2af9ad2484e4077a0bc1a8cd1d30dec,
title = "Calculations of solid-state 43Ca 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 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.",
author = "Holmes, {Sean T.} and Shi Bai and Iuliucci, {Robbie J.} and Mueller, {Karl Todd} and Cecil Dybowski",
year = "2017",
month = "5",
day = "15",
doi = "10.1002/jcc.24763",
language = "English (US)",
volume = "38",
pages = "949--956",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "John Wiley and Sons Inc.",
number = "13",

}

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 journalArticle

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 -