High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions
<jats:title>Abstract</jats:title><jats:p>Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and hi...
| Main Authors: | , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Springer Science and Business Media LLC
2022
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| Online Access: | https://hdl.handle.net/1721.1/144281 |
| _version_ | 1826198683805286400 |
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| author | Spiekermann, Kevin Pattanaik, Lagnajit Green, William H |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Spiekermann, Kevin Pattanaik, Lagnajit Green, William H |
| author_sort | Spiekermann, Kevin |
| collection | MIT |
| description | <jats:title>Abstract</jats:title><jats:p>Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and high-quality datasets are especially rare. Here, we use CCSD(T)-F12a/cc-pVDZ-F12//<jats:italic>ω</jats:italic>B97X-D3/def2-TZVP to obtain high-quality single point calculations for nearly 22,000 unique stable species and transition states. We report the results from these quantum chemistry calculations and extract the barrier heights and reaction enthalpies to create a kinetics dataset of nearly 12,000 gas-phase reactions. These reactions involve H, C, N, and O, contain up to seven heavy atoms, and have cleaned atom-mapped SMILES. Our higher-accuracy coupled-cluster barrier heights differ significantly (RMSE of ∼5 kcal mol<jats:sup>−1</jats:sup>) relative to those calculated at <jats:italic>ω</jats:italic>B97X-D3/def2-TZVP. We also report accurate transition state theory rate coefficients <jats:inline-formula><jats:alternatives><jats:tex-math>$${k}_{\infty }(T)$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML">
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<mml:mi>k</mml:mi>
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<mml:mi>∞</mml:mi>
</mml:mrow>
</mml:msub>
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</mml:math></jats:alternatives></jats:inline-formula> between 300 K and 2000 K and the corresponding Arrhenius parameters for a subset of rigid reactions. We believe this data will accelerate development of automated and reliable methods for quantitative reaction prediction.</jats:p> |
| first_indexed | 2024-09-23T11:08:11Z |
| format | Article |
| id | mit-1721.1/144281 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:08:11Z |
| publishDate | 2022 |
| publisher | Springer Science and Business Media LLC |
| record_format | dspace |
| spelling | mit-1721.1/1442812023-02-06T19:37:46Z High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions Spiekermann, Kevin Pattanaik, Lagnajit Green, William H Massachusetts Institute of Technology. Department of Chemical Engineering <jats:title>Abstract</jats:title><jats:p>Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and high-quality datasets are especially rare. Here, we use CCSD(T)-F12a/cc-pVDZ-F12//<jats:italic>ω</jats:italic>B97X-D3/def2-TZVP to obtain high-quality single point calculations for nearly 22,000 unique stable species and transition states. We report the results from these quantum chemistry calculations and extract the barrier heights and reaction enthalpies to create a kinetics dataset of nearly 12,000 gas-phase reactions. These reactions involve H, C, N, and O, contain up to seven heavy atoms, and have cleaned atom-mapped SMILES. Our higher-accuracy coupled-cluster barrier heights differ significantly (RMSE of ∼5 kcal mol<jats:sup>−1</jats:sup>) relative to those calculated at <jats:italic>ω</jats:italic>B97X-D3/def2-TZVP. We also report accurate transition state theory rate coefficients <jats:inline-formula><jats:alternatives><jats:tex-math>$${k}_{\infty }(T)$$</jats:tex-math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msub> <mml:mrow> <mml:mi>k</mml:mi> </mml:mrow> <mml:mrow> <mml:mi>∞</mml:mi> </mml:mrow> </mml:msub> <mml:mrow> <mml:mo>(</mml:mo> <mml:mrow> <mml:mi>T</mml:mi> </mml:mrow> <mml:mo>)</mml:mo> </mml:mrow> </mml:math></jats:alternatives></jats:inline-formula> between 300 K and 2000 K and the corresponding Arrhenius parameters for a subset of rigid reactions. We believe this data will accelerate development of automated and reliable methods for quantitative reaction prediction.</jats:p> 2022-08-09T15:32:40Z 2022-08-09T15:32:40Z 2022-12 2022-08-09T15:30:25Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/144281 Spiekermann, Kevin, Pattanaik, Lagnajit and Green, William H. 2022. "High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions." Scientific Data, 9 (1). en 10.1038/s41597-022-01529-6 Scientific Data Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf Springer Science and Business Media LLC Scientific Data |
| spellingShingle | Spiekermann, Kevin Pattanaik, Lagnajit Green, William H High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title | High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title_full | High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title_fullStr | High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title_full_unstemmed | High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title_short | High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions |
| title_sort | high accuracy barrier heights enthalpies and rate coefficients for chemical reactions |
| url | https://hdl.handle.net/1721.1/144281 |
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