On the H-atom abstractions from C1-C4 alcohols, aldehydes, and ethers by NO2: ab initio and comprehensive kinetic modeling
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| Main Authors: | , , , , , , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866912118551347200 |
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| author | Wu^, Hongqing Tang^, Ruoyue Dong, Yuxin Ren, Xinrui Wang, Mingrui Zhang, Ting Zhang, Hongjie Feng, Guangyuan Cheng, Song |
| author_facet | Wu^, Hongqing Tang^, Ruoyue Dong, Yuxin Ren, Xinrui Wang, Mingrui Zhang, Ting Zhang, Hongjie Feng, Guangyuan Cheng, Song |
| contents | As crucial additives and intermediate, alcohols, ethers, and aldehydes play a significant role in the combustion process. However, the chemistry of NOXhydrocarbon interactions and the rate rules governing these interactions remain largely unexplored in this combustion system. To address this gap, this study provides a comprehensive investigation of H-atom abstraction by NO2 from C1-C4 alcohols, aldehydes and ethers that leads to the formation of 3 HNO2 isomers (i.e., transHONO, HNO2, and cisHONO), encompassing 9 hydrocarbons and 45 reactions. Utilizing the DLPNO CCSD(T)cc pVDZ M06 2X 6 311g d,p method, the electronic structures, single point energies, C H bond dissociation energies and 1 D hindered rotor potentials of the reactants, transition states, complexes and products in each reaction are computed. Adding these H atom abstractions to the chemical kinetic model improves the model reactivity and advances the ignition, as indicated by the reduction in ignition delay time for species that initially lacked these reactions. Further sensitivity and flux analyses highlight the crucial role of H atom abstraction by NO2. The findings underscore the importance of accurately incorporating these kinetic parameters into newly developed chemical models for alcohols, aldehydes, and ethers. Additionally, the study highlights the need for future experimental efforts to investigate the effects of NO2 on the combustion systems of these compounds. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2411_09207 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | On the H-atom abstractions from C1-C4 alcohols, aldehydes, and ethers by NO2: ab initio and comprehensive kinetic modeling Wu^, Hongqing Tang^, Ruoyue Dong, Yuxin Ren, Xinrui Wang, Mingrui Zhang, Ting Zhang, Hongjie Feng, Guangyuan Cheng, Song Chemical Physics As crucial additives and intermediate, alcohols, ethers, and aldehydes play a significant role in the combustion process. However, the chemistry of NOXhydrocarbon interactions and the rate rules governing these interactions remain largely unexplored in this combustion system. To address this gap, this study provides a comprehensive investigation of H-atom abstraction by NO2 from C1-C4 alcohols, aldehydes and ethers that leads to the formation of 3 HNO2 isomers (i.e., transHONO, HNO2, and cisHONO), encompassing 9 hydrocarbons and 45 reactions. Utilizing the DLPNO CCSD(T)cc pVDZ M06 2X 6 311g d,p method, the electronic structures, single point energies, C H bond dissociation energies and 1 D hindered rotor potentials of the reactants, transition states, complexes and products in each reaction are computed. Adding these H atom abstractions to the chemical kinetic model improves the model reactivity and advances the ignition, as indicated by the reduction in ignition delay time for species that initially lacked these reactions. Further sensitivity and flux analyses highlight the crucial role of H atom abstraction by NO2. The findings underscore the importance of accurately incorporating these kinetic parameters into newly developed chemical models for alcohols, aldehydes, and ethers. Additionally, the study highlights the need for future experimental efforts to investigate the effects of NO2 on the combustion systems of these compounds. |
| title | On the H-atom abstractions from C1-C4 alcohols, aldehydes, and ethers by NO2: ab initio and comprehensive kinetic modeling |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2411.09207 |