Towards high-level theoretical studies of large biodiesel molecules: an ONIOM/RRKM/Master-equation approach to the isomerization and dissociation kinetics of methyl decanoate radicals

The isomerization and dissociation reactions of methyl decanoate (MD) radicals were theoretically investigated by using high-level theoretical calculations based on a two-layer ONIOM method, employing the QCISD(T)/CBS method for the high layer and the M06-2X/6-311++G(d,p) method for the low layer.

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Toward high-level theoretical studies on the reaction kinetics of PAHs growth based on HACA pathway: An ONIOM[G3(MP2,CC)//B3LYP:DFT] method developed

Fuel ◽

10.1016/j.fuel.2021.121052 ◽

2021 ◽

Vol 301 ◽

pp. 121052

Author(s):

Chengcheng Ao ◽

Shanshan Ruan ◽

Wei He ◽

Yi Liu ◽

Chenliang He ◽

...

Keyword(s):

Reaction Kinetics ◽

Theoretical Studies ◽

High Level ◽

Kinetics Of

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Towards high-level theoretical studies of large biodiesel molecules: an ONIOM [QCISD(T)/CBS:DFT] study of hydrogen abstraction reactions of CnH2n+1COOCmH2m+1 + H

Physical Chemistry Chemical Physics ◽

10.1039/c4cp03004d ◽

2015 ◽

Vol 17 (1) ◽

pp. 200-208 ◽

Cited By ~ 16

Author(s):

Lidong Zhang ◽

Peng Zhang

Keyword(s):

Chemical Kinetics ◽

Hydrogen Abstraction ◽

Alkyl Ester ◽

Theoretical Studies ◽

Recent Interest ◽

High Level ◽

Kinetics Of

Recent interest in biodiesel combustion urges the need for the theoretical chemical kinetics of large alkyl ester molecules.

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Mechanistic and kinetics investigations of oligomer formation from Criegee intermediate reactions with hydroxyalkyl hydroperoxides

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-4075-2019 ◽

2019 ◽

Vol 19 (6) ◽

pp. 4075-4091 ◽

Cited By ~ 4

Author(s):

Long Chen ◽

Yu Huang ◽

Yonggang Xue ◽

Zhenxing Shen ◽

Junji Cao ◽

...

Keyword(s):

Theoretical Calculations ◽

Organic Aerosol ◽

Climate Forcing ◽

Phase Reaction ◽

Methyl Group ◽

Consecutive Reactions ◽

Mechanism And Kinetics ◽

High Level ◽

First Time ◽

Kinetics Of

Abstract. Although secondary organic aerosol (SOA) is a major component of PM2.5 and organic aerosol (OA) particles and therefore profoundly influences air quality, climate forcing, and human health, the mechanism of SOA formation via Criegee chemistry is poorly understood. Herein, we perform high-level theoretical calculations to study the gas-phase reaction mechanism and kinetics of four Criegee intermediate (CI) reactions with four hydroxyalkyl hydroperoxides (HHPs) for the first time. The calculated results show that the consecutive reactions of CIs with HHPs are both thermochemically and kinetically favored, and the oligomers contain CIs as chain units. The addition of an −OOH group in HHPs to the central carbon atom of CIs is identified as the most energetically favorable channel, with a barrier height strongly dependent on both CI substituent number (one or two) and position (syn- or anti-). In particular, the introduction of a methyl group into the anti-position significantly increases the rate coefficient, and a dramatic decrease is observed when the methyl group is introduced into the syn-position. These findings are expected to broaden the reactivity profile and deepen our understanding of atmospheric SOA formation processes.

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Oligomerization Reactions of Criegee Intermediates with Hydroxyalkyl Hydroperoxides: Mechanism, Kinetics, and Structure-Reactivity Relationship

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acp-2018-935 ◽

2018 ◽

pp. 1-35 ◽

Cited By ~ 2

Author(s):

Long Chen ◽

Yu Huang ◽

Yonggang Xue ◽

Zhenxing Shen ◽

Junji Cao ◽

...

Keyword(s):

Theoretical Calculations ◽

Climate Forcing ◽

Atmospheric Lifetime ◽

Methyl Group ◽

Criegee Intermediates ◽

Sequential Addition ◽

Structure Reactivity Relationship ◽

High Level ◽

First Time ◽

Kinetics Of

Abstract. Although secondary organic aerosols (SOAs) are major components of PM2.5 and organic aerosol (OA) particles and therefore profoundly influencing air quality, climate forcing and human health, the mechanism of SOAs formation via Criegee chemistry is poorly understood. Herein, we perform high-level theoretical calculations to study the reactivity and kinetics of four Criegee intermediates (CIs) reactions with four hydroxyalkyl hydroperoxides (HHPs) for the first time. The calculated results show that the sequential addition of CIs to HHPs affords oligomers containing CIs as chain units. The addition of -OOH group in HHPs to the central carbon atom of CIs is identified as the most energetically favorable channel, with a barrier height strongly dependent on both, CI substituent number (one or two) and position (syn- or anti-). In particular, the introduction of a methyl group into the anti-position significantly increase the rate coefficient, dramatic decrease is observed when the methyl group is introduced into the syn-position. Based on the collected data, the atmospheric lifetime of anti-CH3CHOO in the presence of HHPs is estimated as ~5.9×103s. These findings are expected to broaden the reactivity proﬁle and deepen our understanding of atmospheric SOAs formation processes.

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