期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 3, 期 9, 页码 1147-1153出版社
AMER CHEMICAL SOC
DOI: 10.1021/jz300336s
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类别
资金
- FANEDD [200932]
- Major State Basic Research Development Programs [2011CB808503]
- [NSFC20973025]
- [NSFC21033002]
To evaluate the significance of the generation of atmospheric hydroxyl radical from reaction of N2O4 with H2O, CASPT2//CASSCF as well as CASPT2//CASSCF/Amber QM/MM approaches were employed to map the minimum-energy profiles of sequential reactions, NO2 dimerization and ground-state intermolecular proton transfer of trans-ONONO2 as well as the photolysis of HONO. A highly efficient ground-state intermolecular proton transfer of trans-ONONO2 is found to dominate the generation of hydroxyl radical under atmospheric conditions. Although proton transfer occurs with high efficiency, the precursor reaction of dimerization producing trans-ONONO2 has to overcome a 17.1 kcal/mol barrier and cannot compete with the barrierless channel of symmetric O2N-NO2 formation from isolated NO2 monomers. Our computations reveal that the photolysis of HONO without a barrier definitely makes significant contributions to the concentration of the atmospheric hydroxyl radical, but its importance is influenced by the lack of trans-ONONO2 isomer in the atmospheric environment.
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