Details
| Original language | English |
|---|---|
| Article number | e25953 |
| Number of pages | 10 |
| Journal | International Journal of Quantum Chemistry |
| Volume | 119 |
| Issue number | 16 |
| Early online date | 5 Apr 2019 |
| Publication status | Published - 15 Aug 2019 |
Abstract
The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs() routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.
Keywords
- benchmarking, extrapolation methods, focal point analysis, noncovalent interactions, open-source
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Atomic and Molecular Physics, and Optics
- Physics and Astronomy(all)
- Condensed Matter Physics
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: International Journal of Quantum Chemistry, Vol. 119, No. 16, e25953, 15.08.2019.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Validating additive correction schemes against gradient-based extrapolations
AU - Kraus, Peter
AU - Frank, Irmgard
N1 - Funding information: This work was carried out on the Leibniz Universität Hannover compute cluster, which is funded by the Leibniz Universität Hannover, the Lower Saxony Ministry of Science and Culture (MWK) and the German Research Association (DFG). PK would like to thank D. A. Obenchain for helpful comments.
PY - 2019/8/15
Y1 - 2019/8/15
N2 - The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs() routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.
AB - The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs() routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.
KW - benchmarking
KW - extrapolation methods
KW - focal point analysis
KW - noncovalent interactions
KW - open-source
UR - http://www.scopus.com/inward/record.url?scp=85063899481&partnerID=8YFLogxK
U2 - 10.1002/qua.25953
DO - 10.1002/qua.25953
M3 - Article
AN - SCOPUS:85063899481
VL - 119
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 16
M1 - e25953
ER -