Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules

Teobald Kupka; Marzena Nieradka; Michal Stachów; Tadeusz Pluta; Piotr Nowak; Hanna Kjær; Jacob Kongsted; Jakub Kaminsky

doi:10.1021/jp212588h

Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules

Teobald Kupka, Marzena Nieradka, Michal Stachów, Tadeusz Pluta, Piotr Nowak, Hanna Kjær, Jacob Kongsted, Jakub Kaminsky

Department of Chemistry

53 Citations (Scopus)

Abstract

The performance of more than 40 density functionals in predicting indirect spin-spin coupling constants (SSCCs) in the Kohn-Sham basis set limit was tested. For comparison, similar calculations were performed using the RHF, SOPPA, SOPPA(CC2), and SOPPA(CCSD) methods, and the results were estimated toward the complete basis set (CBS) limit. The SSCCs of nine small molecules (N ₂, CO, CO ₂, NH ₃, CH ₄, C ₂H ₂, C ₂H ₄, C ₂H ₆, and C ₆H ₆) were calculated using the dedicated Jensen pcJ-n polarization-consistent basis sets and used for the CBS limit estimations within the Kohn-Sham limit. These CBS results were compared with calculations using the aug-cc-pVTZ-J basis set. Among the 41 studied DFT methods, the tHCTHhyb, HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X functionals reproduced accurately the experimental ¹J(XH) SSCCs and ³J(HH60) and ²J(HH _gem) in ethane. Similarly, the functionals HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X predicted accurately ¹J(CC), and B98, B97-1, B97-2, PBE1PBE, B1LYP, and O3LYP provided accurate ¹J(CO) results in the CO molecule. A very good performance for the calculation of the SSCCs based on the use of the relatively small basis set aug-cc-pVTZ-J was observed.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	116
Issue number	14
Pages (from-to)	3728-3738
Number of pages	11
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp212588h
Publication status	Published - 12 Apr 2012

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10.1021/jp212588h

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Kupka, T., Nieradka, M., Stachów, M., Pluta, T., Nowak, P., Kjær, H., Kongsted, J., & Kaminsky, J. (2012). Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 116(14), 3728-3738. https://doi.org/10.1021/jp212588h

Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules. / Kupka, Teobald; Nieradka, Marzena; Stachów, Michal et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 116, No. 14, 12.04.2012, p. 3728-3738.

Research output: Contribution to journal › Journal article › Research › peer-review

Kupka, T, Nieradka, M, Stachów, M, Pluta, T, Nowak, P, Kjær, H, Kongsted, J & Kaminsky, J 2012, 'Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 116, no. 14, pp. 3728-3738. https://doi.org/10.1021/jp212588h

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title = "Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules",

abstract = "The performance of more than 40 density functionals in predicting indirect spin-spin coupling constants (SSCCs) in the Kohn-Sham basis set limit was tested. For comparison, similar calculations were performed using the RHF, SOPPA, SOPPA(CC2), and SOPPA(CCSD) methods, and the results were estimated toward the complete basis set (CBS) limit. The SSCCs of nine small molecules (N 2, CO, CO 2, NH 3, CH 4, C 2H 2, C 2H 4, C 2H 6, and C 6H 6) were calculated using the dedicated Jensen pcJ-n polarization-consistent basis sets and used for the CBS limit estimations within the Kohn-Sham limit. These CBS results were compared with calculations using the aug-cc-pVTZ-J basis set. Among the 41 studied DFT methods, the tHCTHhyb, HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X functionals reproduced accurately the experimental 1J(XH) SSCCs and 3J(HH60) and 2J(HH gem) in ethane. Similarly, the functionals HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X predicted accurately 1J(CC), and B98, B97-1, B97-2, PBE1PBE, B1LYP, and O3LYP provided accurate 1J(CO) results in the CO molecule. A very good performance for the calculation of the SSCCs based on the use of the relatively small basis set aug-cc-pVTZ-J was observed.",

author = "Teobald Kupka and Marzena Nieradka and Michal Stach{\'o}w and Tadeusz Pluta and Piotr Nowak and Hanna Kj{\ae}r and Jacob Kongsted and Jakub Kaminsky",

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doi = "10.1021/jp212588h",

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T1 - Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules

AU - Kupka, Teobald

AU - Nieradka, Marzena

AU - Stachów, Michal

AU - Pluta, Tadeusz

AU - Nowak, Piotr

AU - Kjær, Hanna

AU - Kongsted, Jacob

AU - Kaminsky, Jakub

PY - 2012/4/12

Y1 - 2012/4/12

N2 - The performance of more than 40 density functionals in predicting indirect spin-spin coupling constants (SSCCs) in the Kohn-Sham basis set limit was tested. For comparison, similar calculations were performed using the RHF, SOPPA, SOPPA(CC2), and SOPPA(CCSD) methods, and the results were estimated toward the complete basis set (CBS) limit. The SSCCs of nine small molecules (N 2, CO, CO 2, NH 3, CH 4, C 2H 2, C 2H 4, C 2H 6, and C 6H 6) were calculated using the dedicated Jensen pcJ-n polarization-consistent basis sets and used for the CBS limit estimations within the Kohn-Sham limit. These CBS results were compared with calculations using the aug-cc-pVTZ-J basis set. Among the 41 studied DFT methods, the tHCTHhyb, HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X functionals reproduced accurately the experimental 1J(XH) SSCCs and 3J(HH60) and 2J(HH gem) in ethane. Similarly, the functionals HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X predicted accurately 1J(CC), and B98, B97-1, B97-2, PBE1PBE, B1LYP, and O3LYP provided accurate 1J(CO) results in the CO molecule. A very good performance for the calculation of the SSCCs based on the use of the relatively small basis set aug-cc-pVTZ-J was observed.

AB - The performance of more than 40 density functionals in predicting indirect spin-spin coupling constants (SSCCs) in the Kohn-Sham basis set limit was tested. For comparison, similar calculations were performed using the RHF, SOPPA, SOPPA(CC2), and SOPPA(CCSD) methods, and the results were estimated toward the complete basis set (CBS) limit. The SSCCs of nine small molecules (N 2, CO, CO 2, NH 3, CH 4, C 2H 2, C 2H 4, C 2H 6, and C 6H 6) were calculated using the dedicated Jensen pcJ-n polarization-consistent basis sets and used for the CBS limit estimations within the Kohn-Sham limit. These CBS results were compared with calculations using the aug-cc-pVTZ-J basis set. Among the 41 studied DFT methods, the tHCTHhyb, HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X functionals reproduced accurately the experimental 1J(XH) SSCCs and 3J(HH60) and 2J(HH gem) in ethane. Similarly, the functionals HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X predicted accurately 1J(CC), and B98, B97-1, B97-2, PBE1PBE, B1LYP, and O3LYP provided accurate 1J(CO) results in the CO molecule. A very good performance for the calculation of the SSCCs based on the use of the relatively small basis set aug-cc-pVTZ-J was observed.

U2 - 10.1021/jp212588h

DO - 10.1021/jp212588h

M3 - Journal article

C2 - 22401301

SN - 1089-5639

VL - 116

SP - 3728

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JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 14

ER -

Basis set convergence of indirect spin–spin coupling constants in the Kohn–Sham limit for several small molecules

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