Oxygen Insertion Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether
ORAL
Abstract
In situ laser spectroscopy, quantum chemistry, and kinetic calculations are integrated to study the reaction of photolytically generated singlet oxygen atoms with dimethyl ether in a well-characterized flow reactor. This is an initiation and branching reaction which is important in the gas-phase plasma chemistry. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products. Fitting temporal profiles of products with simulations allows product branching to be quantified and the major channel yields two CH3O radicals. The experimentally determined product branching agrees well with master equation calculations,which show that a weakly bound charge transfer complex (CH3OOCH3) is formed by O insertion into the C-O bond. This O insertion mechanism can be important for understanding the plasma-based biofuel processing technologies.
*Research at Princeton University is primarily supported by the U.S. Department of Energy, Office of Science Energy Earthshot Initiative as part of Plasma-Enhanced H2 Production(PEHPr) Energy Earthshot Research Center (EERC) at Princeton Plasma Physics Laboratory under contract DE-AC0209CH11466., Hongtao Zhong and Bowen Mei are partlysupported by DOE grant DE-SC0020233 of Plasma Science Center and NSF grant EFMA 2029425. The work at the University of Minnesota was supported in part by the U.S.Department of Energy, Office of Basic Energy Sciences under Award DE-SC0015997.
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Publication:Zhong, Hongtao, et al. "Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether." The Journal of Physical Chemistry Letters 15 (2024): 6158-6165.
Presenters
Hongtao Zhong
Stanford University
Authors
Hongtao Zhong
Stanford University
Qinghui Meng
Department of Chemistry and Chemical Theory Center, University of Minnesota
