Ground-State Intermolecular Proton Transfer of N2O4 and H2O: An Important Source of Atmospheric Hydroxyl Radical?
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- 作者：Gefei Luo ; Xuebo Chen
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2012
- 出版时间：May 3, 2012
- 年：2012
- 卷：3
- 期：9
- 页码：1147-1153
- 全文大小：431K
- 年卷期：v.3,no.9(May 3, 2012)
- ISSN：1948-7185
文摘
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鈥揘O2 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.