TY - JOUR
T1 - Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether
AU - Zhong, Hongtao
AU - Meng, Qinghui
AU - Mei, Bowen
AU - Thawko, Andy
AU - Yan, Chao
AU - LIU, Ning
AU - Mao, Xingqian
AU - Wang, Ziyu
AU - Wysocki, Gerard
AU - Truhlar, Donald G.
AU - Ju, Yiguang
PY - 2024/6/13
Y1 - 2024/6/13
N2 - We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C–O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.© 2024 American Chemical Society
AB - We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C–O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.© 2024 American Chemical Society
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U2 - 10.1021/acs.jpclett.4c00907
DO - 10.1021/acs.jpclett.4c00907
M3 - RGC 21 - Publication in refereed journal
SN - 1948-7185
VL - 15
SP - 6158
EP - 6165
JO - The Journal of Physical Chemistry Letters
JF - The Journal of Physical Chemistry Letters
ER -
