Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions
The chemical kinetics of hydrogen atom (H-atom) abstraction reactions from norbornadiene (NBD) by five radicals (H, O(3P), OH, CH3, and HO2), and the unimolecular reactions of three NBD derived radicals, were studied through high-level ab-initio calculations. The geometries optimization and vibratio...
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| Format: | Article |
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KeAi Communications Co., Ltd.
2023-03-01
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| Series: | Propulsion and Power Research |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2212540X23000135 |
| _version_ | 1797703575907860480 |
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| author | Jintao Chen Mingxia Liu Yuxiang Zhu Kairu Jin Zhenyu Tian Lijun Yang Chong-Wen Zhou |
| author_facet | Jintao Chen Mingxia Liu Yuxiang Zhu Kairu Jin Zhenyu Tian Lijun Yang Chong-Wen Zhou |
| author_sort | Jintao Chen |
| collection | DOAJ |
| description | The chemical kinetics of hydrogen atom (H-atom) abstraction reactions from norbornadiene (NBD) by five radicals (H, O(3P), OH, CH3, and HO2), and the unimolecular reactions of three NBD derived radicals, were studied through high-level ab-initio calculations. The geometries optimization and vibrational frequencies calculation for all the reactants, transition states, and products were obtained at the M06-2X/6-311++G(d,p) level of theory. The zero-point energy (ZPE) corrected potential energy surfaces (PESs) were determined at the QCISD(T)/cc-pVDZ, TZ level of theory with basis set corrections from MP2/cc-pVDZ, TZ, QZ methods for single point energy calculations. Conventional transition state theory (TST) was used for the rate constants calculations of H-atom abstraction reactions by five radicals (H, O(3P), OH, CH3, and HO2) at temperatures from 298.15 to 2000 K, while the α-site H-atom abstraction reaction rate constant of NBD by OH radical has been obtained through variational transition state theory (VTST). The results show that the H-atom abstraction reactions from the α-carbon atom of NBD are the most critical channels at low temperatures. Total rate constants for H-atom abstraction reactions by OH radical are also the fastest among all of the reaction channels investigated at the temperature range from 298.15 to 2000 K. Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) has been used to calculate the pressure- and temperature-dependent rate constants for the unimolecular reactions of three related C7H7 product radicals which generated from H-atom abstraction reaction within temperature ranges of 300–2000 K and pressures of 0.01–100 atm. A combination of composite methods has been used to calculate the temperature-dependent thermochemical properties of NBD and related radicals. All the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation. |
| first_indexed | 2024-03-12T05:07:34Z |
| format | Article |
| id | doaj.art-3e9330253c994f53864ee982e960d3f6 |
| institution | Directory Open Access Journal |
| issn | 2212-540X |
| language | English |
| last_indexed | 2024-03-12T05:07:34Z |
| publishDate | 2023-03-01 |
| publisher | KeAi Communications Co., Ltd. |
| record_format | Article |
| series | Propulsion and Power Research |
| spelling | doaj.art-3e9330253c994f53864ee982e960d3f62023-09-03T08:53:11ZengKeAi Communications Co., Ltd.Propulsion and Power Research2212-540X2023-03-01121104113Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactionsJintao Chen0Mingxia Liu1Yuxiang Zhu2Kairu Jin3Zhenyu Tian4Lijun Yang5Chong-Wen Zhou6School of Energy and Power Engineering, Beihang University, Beijing 100191, ChinaSchool of Energy and Power Engineering, Beihang University, Beijing 100191, ChinaSchool of Energy and Power Engineering, Beihang University, Beijing 100191, ChinaInstitute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China; University of Chinese Academy of Sciences, Beijing 100049, ChinaInstitute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China; University of Chinese Academy of Sciences, Beijing 100049, ChinaSchool of Astronautics, Beihang University, Beijing 100191, ChinaSchool of Energy and Power Engineering, Beihang University, Beijing 100191, China; Combustion Chemistry Centre, School of Biological and Chemical Sciences, University of Galway, Galway H91TK33, Ireland; Corresponding author.The chemical kinetics of hydrogen atom (H-atom) abstraction reactions from norbornadiene (NBD) by five radicals (H, O(3P), OH, CH3, and HO2), and the unimolecular reactions of three NBD derived radicals, were studied through high-level ab-initio calculations. The geometries optimization and vibrational frequencies calculation for all the reactants, transition states, and products were obtained at the M06-2X/6-311++G(d,p) level of theory. The zero-point energy (ZPE) corrected potential energy surfaces (PESs) were determined at the QCISD(T)/cc-pVDZ, TZ level of theory with basis set corrections from MP2/cc-pVDZ, TZ, QZ methods for single point energy calculations. Conventional transition state theory (TST) was used for the rate constants calculations of H-atom abstraction reactions by five radicals (H, O(3P), OH, CH3, and HO2) at temperatures from 298.15 to 2000 K, while the α-site H-atom abstraction reaction rate constant of NBD by OH radical has been obtained through variational transition state theory (VTST). The results show that the H-atom abstraction reactions from the α-carbon atom of NBD are the most critical channels at low temperatures. Total rate constants for H-atom abstraction reactions by OH radical are also the fastest among all of the reaction channels investigated at the temperature range from 298.15 to 2000 K. Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) has been used to calculate the pressure- and temperature-dependent rate constants for the unimolecular reactions of three related C7H7 product radicals which generated from H-atom abstraction reaction within temperature ranges of 300–2000 K and pressures of 0.01–100 atm. A combination of composite methods has been used to calculate the temperature-dependent thermochemical properties of NBD and related radicals. All the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation.http://www.sciencedirect.com/science/article/pii/S2212540X23000135NorbornadieneAb-initio calculationsRate constantsKineticThermochemistry |
| spellingShingle | Jintao Chen Mingxia Liu Yuxiang Zhu Kairu Jin Zhenyu Tian Lijun Yang Chong-Wen Zhou Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions Propulsion and Power Research Norbornadiene Ab-initio calculations Rate constants Kinetic Thermochemistry |
| title | Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions |
| title_full | Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions |
| title_fullStr | Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions |
| title_full_unstemmed | Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions |
| title_short | Oxidation of norbornadiene: Theoretical investigation on H-atom abstraction and related radical decomposition reactions |
| title_sort | oxidation of norbornadiene theoretical investigation on h atom abstraction and related radical decomposition reactions |
| topic | Norbornadiene Ab-initio calculations Rate constants Kinetic Thermochemistry |
| url | http://www.sciencedirect.com/science/article/pii/S2212540X23000135 |
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