Strong dependence on multistructural anharmonicity of the relative rates of intramolecular H-migration in alkylperoxyl and methylcyclohexylperoxyl radicals

Lili Xing; Liuchao Lian; Donald G. Truhlar

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Strong dependence on multistructural anharmonicity of the relative rates of intramolecular H-migration in alkylperoxyl and methylcyclohexylperoxyl radicals

机译：Strong dependence on multistructural anharmonicity of the relative rates of intramolecular H-migration in alkylperoxyl and methylcyclohexylperoxyl radicals

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Alkylperoxyl (RO 2 ) and hydroperoxyalkyl (QOOH) species are crucial intermediates produced duringthe autoignition of transport fuels, and consequently their thermodynamic and kinetic data are veryimportant. Since these data are not available experimentally, we take up the challenge of computingthem from first principles. We compare the 1,5 shifts in 2-methyl-4-heptylperoxyl radical and 3-methylcyclohexylperoxy radical to clarify the similarities and differences of the kinetics of chain alkanesand cycloalkanes in the fuel oxidation mechanism. In order to take account of the multistructural andcoupled torsional anharmonicity, we employ multistructural canonical variational transition state theory(MS-VTST) with multidimensional tunneling to calculate rate constants. The calculations explicitly includeall conformers: 6 and 154 for the two reactants, 7, 6, 1, and 1 for the four transition states, and 289, 282,8, and 5 for the four products (which are the reactants for the reverse reactions). The effects of variousfactors on the thermodynamic data and calculated rate constants are evaluated in detail. We foundthat multistructural torsional anharmonicity has a very large effect on the rate constants. This work illustrateshow modern density functional and dynamics methods make it possible to calculate accurate rateconstants for both branched-chain and cycloalkane peroxy radicals and hydroperoxy species.

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来源
《Combustion and Flame》 |2021年第9期|111503.1-111503.12|共12页
作者
Lili Xing; Liuchao Lian; Donald G. Truhlar;
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作者单位

Energy and Power Engineering Institute, Henan University of Science and Technology, Luoyang, Henan 471003, China;

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

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收录信息美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);
原文格式 PDF
正文语种英语
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Alkylperoxyl (RO 2 ); Cycloalkylperoxyl; Autoignition; Quantum chemical calculations; Kinetics; Torsional anharmonicity;

Strong dependence on multistructural anharmonicity of the relative rates of intramolecular H-migration in alkylperoxyl and methylcyclohexylperoxyl radicals

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