首页|Unimolecular Reactions of E-Glycolaldehyde Oxide and Its Reactions with One and Two Water Molecules

Unimolecular Reactions of E-Glycolaldehyde Oxide and Its Reactions with One and Two Water Molecules

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The kinetics of Criegee intermediates are important for atmospheric modeling.However,the quantitative kinetics of Criegee intermediates are still very limited,especially for those with hydroxy groups.Here,we calculate rate constants for the unimolecular reaction of E-glycolaldehyde oxide[E-hydroxyethanal oxide,E-(CH20H)CH00],for its reactions with H20 and(H20)2,and for the reaction of the E-(CH2OH)CHOO...H20 complex with H20.For the highest level of electronic structure,we use W3X-L//CCSD(T)-F12a/cc-pVDZ-F12 for the unimolecular reaction and the reaction with water and W3X-L//DF-CCSD(T)-F12b/jun-cc-pVDZ for the reaction with 2 water molecules.For the dynamics,we use a dual-level strategy that combines conventional transition state theory with the highest level of electronic structure and multistructural canonical variational transition state theory with small-curvature tunneling with a validated density functional for the electronic structure.This dynamical treatment includes high-frequency anharmonicity,torsional anharmonicity,recrossing effects,and tunneling.We find that the unimolecular reaction of E-(CH20H)CHOO depends on both temperature and pressure.The calculated results show that E-(CH20H)CHOO...H20+H20 is the dominant entrance channel,while previous investigations only considered Criegee intermediates+(H20)2.In addition,we find that the atmospheric lifetime of E-(CH20H)CHOO with respect to 2 water molecules is particularly short with a value of 1.71 × 10-6 s at 0 km,which is about 2 orders of magnitude shorter than those usually assumed for Criegee intermediate reactions with water dimer.We also find that the OH group in E-(CH20H)CHOO enhances its reactivity.

Yan Sun、Bo Long、Donald G.Truhlar

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Department of Physics,Guizhou University,Guiyang 550025,China

College of Materials Science and Engineering,Guizhou Minzu University,Guiyang 550025,China

Department of Chemistry,Chemical Theory Center,and Supercomputing Institute,University of Minnesota,Minneapolis,MN 55455-0431,USA

国家自然科学基金国家自然科学基金国家自然科学基金Guizhou Provincial Science and Technology Projects,ChinaScience and Technology Foundation of Guizhou Provincial Department of Education,ChinaU.S.Department of Energy,Office of Science,Office of Basic Energy Sciences

421201040074177512591961123CXTD[2022]001KY[2021]014Award DE-SC0015997

2024

10.34133/research.0143

研究(英文)

研究(英文)

CSTPCD
ISSN：
年,卷(期)：2024.2024(1)
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