A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity

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Standard

A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity. / Pedersen, Jacob; Mikkelsen, Kurt V.

I: RSC Advances, Bind 12, Nr. 5, 2022, s. 2830-2842.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Pedersen, J & Mikkelsen, KV 2022, 'A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity', RSC Advances, bind 12, nr. 5, s. 2830-2842. https://doi.org/10.1039/d2ra00093h

APA

Pedersen, J., & Mikkelsen, K. V. (2022). A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity. RSC Advances, 12(5), 2830-2842. https://doi.org/10.1039/d2ra00093h

Vancouver

Pedersen J, Mikkelsen KV. A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity. RSC Advances. 2022;12(5):2830-2842. https://doi.org/10.1039/d2ra00093h

Author

Pedersen, Jacob ; Mikkelsen, Kurt V. / A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity. I: RSC Advances. 2022 ; Bind 12, Nr. 5. s. 2830-2842.

Bibtex

@article{9762ca7f47ee4d448be3b88c72eea5c6,
title = "A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity",
abstract = "Five different aromaticity indexes are benchmarked for benzene, pyridine and the diazines in their ground states. A basis set study was performed using the Pople style, Karlsruhe and Dunning's correlation consistent basis sets. Ten different DFT functionals, including LSDA, PBE, PBE0, B3LYP, CAM-B3LYP, wB97XD, M06-2X, SOGGA11X, M11 and MN15 were benchmarked by comparison with CCSD, CASSCF and MP2. Large out-of-plane imaginary frequencies were observed for some of the optimized structures at the correlated wavefunction level of theory. It was found that the DFT functionals in general predict the para-delocalization index, multicenter index and aromatic fluctuation index to be approximately 70%, 50% and 45% larger, respectively, compared to the CCSD method. Comparisons of the DFT functionals showed that the wB97XD, CAM-B3LYP and M06-2X functionals performed the best. Furthermore, the basis set dependence of the DFT functionals was found to be large for the electron sharing indexes. Based on these findings, it is recommended to perform ground state calculations of aromaticity indexes at the wB97XD, CAM-B3LYP or M06-2X level of theory utilizing a simple basis set of triple-ζ quality.",
author = "Jacob Pedersen and Mikkelsen, {Kurt V.}",
year = "2022",
doi = "10.1039/d2ra00093h",
language = "English",
volume = "12",
pages = "2830--2842",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "RSC Publishing",
number = "5",

}

RIS

TY - JOUR

T1 - A benchmark study of aromaticity indexes for benzene, pyridine and the diazines – I. Ground state aromaticity

AU - Pedersen, Jacob

AU - Mikkelsen, Kurt V.

PY - 2022

Y1 - 2022

N2 - Five different aromaticity indexes are benchmarked for benzene, pyridine and the diazines in their ground states. A basis set study was performed using the Pople style, Karlsruhe and Dunning's correlation consistent basis sets. Ten different DFT functionals, including LSDA, PBE, PBE0, B3LYP, CAM-B3LYP, wB97XD, M06-2X, SOGGA11X, M11 and MN15 were benchmarked by comparison with CCSD, CASSCF and MP2. Large out-of-plane imaginary frequencies were observed for some of the optimized structures at the correlated wavefunction level of theory. It was found that the DFT functionals in general predict the para-delocalization index, multicenter index and aromatic fluctuation index to be approximately 70%, 50% and 45% larger, respectively, compared to the CCSD method. Comparisons of the DFT functionals showed that the wB97XD, CAM-B3LYP and M06-2X functionals performed the best. Furthermore, the basis set dependence of the DFT functionals was found to be large for the electron sharing indexes. Based on these findings, it is recommended to perform ground state calculations of aromaticity indexes at the wB97XD, CAM-B3LYP or M06-2X level of theory utilizing a simple basis set of triple-ζ quality.

AB - Five different aromaticity indexes are benchmarked for benzene, pyridine and the diazines in their ground states. A basis set study was performed using the Pople style, Karlsruhe and Dunning's correlation consistent basis sets. Ten different DFT functionals, including LSDA, PBE, PBE0, B3LYP, CAM-B3LYP, wB97XD, M06-2X, SOGGA11X, M11 and MN15 were benchmarked by comparison with CCSD, CASSCF and MP2. Large out-of-plane imaginary frequencies were observed for some of the optimized structures at the correlated wavefunction level of theory. It was found that the DFT functionals in general predict the para-delocalization index, multicenter index and aromatic fluctuation index to be approximately 70%, 50% and 45% larger, respectively, compared to the CCSD method. Comparisons of the DFT functionals showed that the wB97XD, CAM-B3LYP and M06-2X functionals performed the best. Furthermore, the basis set dependence of the DFT functionals was found to be large for the electron sharing indexes. Based on these findings, it is recommended to perform ground state calculations of aromaticity indexes at the wB97XD, CAM-B3LYP or M06-2X level of theory utilizing a simple basis set of triple-ζ quality.

U2 - 10.1039/d2ra00093h

DO - 10.1039/d2ra00093h

M3 - Journal article

C2 - 35425306

VL - 12

SP - 2830

EP - 2842

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 5

ER -

ID: 291119713