A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake
Polyphenolic compounds are now widely studied using computational chemistry approaches, the most popular of which is Density Functional Theory. To ease this process, it is critical to identify the optimal level of theory in terms of both accuracy and resource usage—a challenge we tackle in this stud...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/16/5058 |
| _version_ | 1797522678042591232 |
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| author | Maciej Spiegel Andrzej Gamian Zbigniew Sroka |
| author_facet | Maciej Spiegel Andrzej Gamian Zbigniew Sroka |
| author_sort | Maciej Spiegel |
| collection | DOAJ |
| description | Polyphenolic compounds are now widely studied using computational chemistry approaches, the most popular of which is Density Functional Theory. To ease this process, it is critical to identify the optimal level of theory in terms of both accuracy and resource usage—a challenge we tackle in this study. Eleven DFT functionals with varied Hartree–Fock exchange values, both global and range-separated hybrids, were combined with 14 differently augmented basis sets to calculate the reactivity indices of caffeic acid, a phenolic acid representative, and compare them to experimental data or a high-level of theory outcome. Aside from the main course, a validation of the widely used Janak’s theorem in the establishment of vertical ionization potential and vertical electron affinity was evaluated. To investigate what influences the values of the properties under consideration, linear regression models were developed and thoroughly discussed. The results were utilized to compute the scores, which let us determine the best and worst combinations and make broad suggestions on the final option. The study demonstrates that M06–2X/6–311G(d,p) is the best fit for such research, and, curiously, it is not necessarily essential to include a diffuse function to produce satisfactory results. |
| first_indexed | 2024-03-10T08:31:51Z |
| format | Article |
| id | doaj.art-0e91a8dd2a614a669076c25b7e509743 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T08:31:51Z |
| publishDate | 2021-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-0e91a8dd2a614a669076c25b7e5097432023-11-22T08:56:00ZengMDPI AGMolecules1420-30492021-08-012616505810.3390/molecules26165058A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources UptakeMaciej Spiegel0Andrzej Gamian1Zbigniew Sroka2Department of Pharmacognosy and Herbal Medicines, Wroclaw Medical University, Borowska 211A, 50-556 Wroclaw, PolandHirszfeld Institute of Immunology and Experimental Therapy, Polish Academy of Sciences, Rudolfa Weigla 12, 53-114 Wroclaw, PolandDepartment of Pharmacognosy and Herbal Medicines, Wroclaw Medical University, Borowska 211A, 50-556 Wroclaw, PolandPolyphenolic compounds are now widely studied using computational chemistry approaches, the most popular of which is Density Functional Theory. To ease this process, it is critical to identify the optimal level of theory in terms of both accuracy and resource usage—a challenge we tackle in this study. Eleven DFT functionals with varied Hartree–Fock exchange values, both global and range-separated hybrids, were combined with 14 differently augmented basis sets to calculate the reactivity indices of caffeic acid, a phenolic acid representative, and compare them to experimental data or a high-level of theory outcome. Aside from the main course, a validation of the widely used Janak’s theorem in the establishment of vertical ionization potential and vertical electron affinity was evaluated. To investigate what influences the values of the properties under consideration, linear regression models were developed and thoroughly discussed. The results were utilized to compute the scores, which let us determine the best and worst combinations and make broad suggestions on the final option. The study demonstrates that M06–2X/6–311G(d,p) is the best fit for such research, and, curiously, it is not necessarily essential to include a diffuse function to produce satisfactory results.https://www.mdpi.com/1420-3049/26/16/5058density functional theorypolyphenolscomputational chemistrybenchmarkcaffeic acidHartree–Fock exchange |
| spellingShingle | Maciej Spiegel Andrzej Gamian Zbigniew Sroka A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake Molecules density functional theory polyphenols computational chemistry benchmark caffeic acid Hartree–Fock exchange |
| title | A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake |
| title_full | A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake |
| title_fullStr | A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake |
| title_full_unstemmed | A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake |
| title_short | A Statistically Supported Antioxidant Activity DFT Benchmark—The Effects of Hartree–Fock Exchange and Basis Set Selection on Accuracy and Resources Uptake |
| title_sort | statistically supported antioxidant activity dft benchmark the effects of hartree fock exchange and basis set selection on accuracy and resources uptake |
| topic | density functional theory polyphenols computational chemistry benchmark caffeic acid Hartree–Fock exchange |
| url | https://www.mdpi.com/1420-3049/26/16/5058 |
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