Characterization and Activity of CH3OOH and CH3CH2OOH Study on a Photoelectron Spectroscopy

Li, Yimin; Qiao, Sun; Li, Haiyang; Ge, Maofa; Wang, Dianxun

doi:10.1002/cjoc.200590993

Cited by 4 publications

(2 citation statements)

References 27 publications

(14 reference statements)

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“…82 ± 0.03 eV, in good agreement with the 9.87 eV by Yi-Min et al12 The other conformer of CH300H+ is 0.30 eV higher in energy and differs in the dihedral angle of the O-OH hindered rotor. As also suggested by the experiments, we found that CH300H+ can undergo the following simple bond scission reactions: the following section, we discuss the key properties of each channel, while more details and figures are provided in the SI-2 part of the Supporting Information.…”

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confidence: 89%

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Covert

Voronova

Torma

et al. 2018

Phys. Chem. Chem. Phys.

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The dissociative photoionization processes of methyl hydroperoxide (CH3OOH) have been studied by imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy experiments as well as quantum-chemical and statistical rate calculations. Energy selected CH3OOH+ ions dissociate into CH2OOH+, HCO+, CH3+, and H3O+ ions in the 11.4-14.0 eV photon energy range. The lowest-energy dissociation channel is the formation of the cation of the smallest "QOOH" radical, CH2OOH+. An extended RRKM model fitted to the experimental data yields a 0 K appearance energy of 11.647 ± 0.005 eV for the CH2OOH+ ion, and a 74.2 ± 2.6 kJ mol-1 mixed experimental-theoretical 0 K heat of formation for the CH2OOH radical. The proton affinity of the Criegee intermediate, CH2OO, was also obtained from the heat of formation of CH2OOH+ (792.8 ± 0.9 kJ mol-1) to be 847.7 ± 1.1 kJ mol-1, reducing the uncertainty of the previously available computational value by a factor of 4. RRKM modeling of the complex web of possible rearrangement-dissociation processes was used to model the higher-energy fragmentation. Supported by Born-Oppenheimer molecular dynamics simulations, we found that the HCO+ fragment ion is produced through a roaming transition state followed by a low barrier. H3O+ is formed in a consecutive process from the CH2OOH+ fragment ion, while direct C-O fission of the molecular ion leads to the methyl cation.

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supporting

confidence: 89%

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Covert

Voronova

Torma

et al. 2018

Phys. Chem. Chem. Phys.

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“…Concentrations of these organic peroxides in the atmosphere depend not only on their sources, but also on their chemical conversions, which determine their sinks. To date, a number of studies on the atmospheric chemical reactions of MHP and EHP have been carried out 5–21…”

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confidence: 99%

Theoretical study on the kinetics of OH radical reactions with CH₃OOH and CH₃CH₂OOH

et al. 2010

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The mechanisms and kinetics studies of the OH radical with alkyl hydroperoxides CH(3)OOH and CH(3)CH(2)OOH reactions have been carried out theoretically. The geometries and frequencies of all the stationary points are calculated at the UBHandHLYP/6-311G(d,p) level, and the energy profiles are further refined by interpolated single-point energies method at the MC-QCISD level of theory. For two reactions, five H-abstraction channels are found and five products (CH(3)OO, CH(2)OOH, CH(3)CH(2)OO, CH(2)CH(2)OOH, and CH(3)CHOOH) are produced during the above processes. The rate constants for the CH(3)OOH/CH(3)CH(2)OOH + OH reactions are corrected by canonical variational transition state theory within 250-1500 K, and the small-curvature tunneling is included. The total rate constants are evaluated from the sum of the individual rate constants and the branching ratios are in good agreement with the experimental data. The Arrhenius expressions for the reactions are obtained.

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Self-reaction of C2H5O2 and its cross-reaction with HO2 studied with vacuum ultraviolet photoionization mass spectrometry

Wen

Hao

Zhang

et al. 2022

Chemical Physics Letters

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Characterization and Activity of CH₃OOH and CH₃CH₂OOH Study on a Photoelectron Spectroscopy

Cited by 4 publications

References 27 publications

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Theoretical study on the kinetics of OH radical reactions with CH₃OOH and CH₃CH₂OOH

Self-reaction of C2H5O2 and its cross-reaction with HO2 studied with vacuum ultraviolet photoionization mass spectrometry

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Characterization and Activity of CH3OOH and CH3CH2OOH Study on a Photoelectron Spectroscopy

Cited by 4 publications

References 27 publications

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Thermochemistry of the smallest QOOH radical from the roaming fragmentation of energy selected methyl hydroperoxide ions

Theoretical study on the kinetics of OH radical reactions with CH3OOH and CH3CH2OOH

Self-reaction of C2H5O2 and its cross-reaction with HO2 studied with vacuum ultraviolet photoionization mass spectrometry

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Characterization and Activity of CH₃OOH and CH₃CH₂OOH Study on a Photoelectron Spectroscopy

Theoretical study on the kinetics of OH radical reactions with CH₃OOH and CH₃CH₂OOH