The Best DFT Functional for the Prediction of 1H and 13C Chemical Shifts of Protonated Alkylpyrroles
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The Best DFT Functional for the Prediction of 1H and 13C Chemical Shifts of Protonated Alkylpyrroles. / Zahn, Sarah L. V.; Hammerich, Ole; Hansen, Poul Erik; Sauer, Stephan P. A.
In: Journal of Computational Chemistry, Vol. 42, No. 18, 25.05.2021, p. 1248-1262.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - The Best DFT Functional for the Prediction of 1H and 13C Chemical Shifts of Protonated Alkylpyrroles
AU - Zahn, Sarah L. V.
AU - Hammerich, Ole
AU - Hansen, Poul Erik
AU - Sauer, Stephan P. A.
PY - 2021/5/25
Y1 - 2021/5/25
N2 - The prediction of 13C chemical shifts can be challenging with density functionaltheory (DFT). In this study 39 different functionals and 3 different basis sets were tested on three neutral alkylpyrroles and their corresponding protonated species. The calculated shielding constants were compared to experimental data and results from previous calculations at the MP2. We find that the meta-hybrid functional TPSSh with either the Pople style basis set 6-311++G(2d,p) or the polarization consistent basis set pcSseg-1 gives the best results for the 13C chemical shifts, whereas for the 1H chemical shifts it is the TPSSh functional with either the 6-311++G(2d,p) or pcSseg-2 basis set. Including an explicit solvent molecule hydrogen bonded to NH in the alkylpyrroles improves the results slightly for the 13C chemical shifts. On the other hand, for 1H chemical shifts the opposite is true. Compared to calculations at the MP2 level none of the DFT functionals can compete with MP2 for the 13C chemical shifts but for the 1H chemical shifts the investigated DFT functionals are shown to give better agreement with experiment than MP2 calculations.
AB - The prediction of 13C chemical shifts can be challenging with density functionaltheory (DFT). In this study 39 different functionals and 3 different basis sets were tested on three neutral alkylpyrroles and their corresponding protonated species. The calculated shielding constants were compared to experimental data and results from previous calculations at the MP2. We find that the meta-hybrid functional TPSSh with either the Pople style basis set 6-311++G(2d,p) or the polarization consistent basis set pcSseg-1 gives the best results for the 13C chemical shifts, whereas for the 1H chemical shifts it is the TPSSh functional with either the 6-311++G(2d,p) or pcSseg-2 basis set. Including an explicit solvent molecule hydrogen bonded to NH in the alkylpyrroles improves the results slightly for the 13C chemical shifts. On the other hand, for 1H chemical shifts the opposite is true. Compared to calculations at the MP2 level none of the DFT functionals can compete with MP2 for the 13C chemical shifts but for the 1H chemical shifts the investigated DFT functionals are shown to give better agreement with experiment than MP2 calculations.
KW - Faculty of Science
KW - density functional theory
KW - DFT calculation
KW - chemical shift
KW - Chemical shielding
KW - NMR spectroscopy
KW - alkylpyrroles
U2 - 10.1002/jcc.26540
DO - 10.1002/jcc.26540
M3 - Journal article
C2 - 33931893
VL - 42
SP - 1248
EP - 1262
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 18
ER -
ID: 258498967