Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autoxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that may precipitate in clouds and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reaction with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C( - O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in particular H atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunneling (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01-100 atm. The accurate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.
Bibliographical noteFunding Information:
This work was supported in part by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award Number DE-SC0015997, by National Key Research and Development Program of China (No. 2016YFC0202600), by National Natural Science Foundation of China (No. 91541112), by the China Scholarship Fund, and by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3022, and Saudi Aramco under the FUELCOM program. J.L.B. acknowledges the financial support from the doctoral dissertation fellowship (DDF) provided by University of Minnesota.
© 2017 American Chemical Society.