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Ultraviolet photodissociation dynamics of 2-methylallyl radical from the 3p Rydberg state were investigated in the wavelength region of 226–244 nm using the high-n Rydberg atom time-of-flight (HRTOF) technique. The 2-methylallyl radicals were generated by 193 nm photolysis of 3-chloro-2-methyl-1-propene precursors. The photofragment yield spectrum of H-atom products increases in intensity with decreasing wavelengths in 226–244 nm. The TOF spectra of H-atom products show a bimodal structure. The predominant product channel (with ∼98% branching ratio) has a kinetic energy release peaking at ∼7 kcal/mol, with an average ratio of ET in the total available energy, (fT), of ∼0.18 in 226–244 nm and an isotropic product angular distribution. At the low ET, isotropic component is from statistical unimolecular decomposition of highly vibrationally excited hot 2-methylallyl to the methylenecyclopropane+H products, following internal conversion from the excited electronic state. The minor product channel (with ∼2% branching ratio) has a large kinetic energy peaking at ∼50 kcal/mol, with (fT)≈0.63 and an anisotropic angular distribution (β≈−0.2). At the high ET, anisotropic component is non-statistical and is postulated to be from direct loss of H atom via the 3p Rydberg state or repulsive part of the ground state to the 1,3-butadiene+H products.
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Kinetics of the a-C 3 H 5 + O 2 reaction, investigated by photoionization using synchrotron radiation
The kinetics of the combustion-relevant reaction of the allyl radical, a-C 3 H 5 , with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring, using the CRF-PEPICO (Combustion Reactions Followed by Photoelectron Photoion Coincidence Spectroscopy) setup. The ability to measure threshold photoelectron spectra enables a background-free detection of reactive species as well as an isomer-specific analysis of reaction products. Allyl was generated by direct photodissociation of allyl iodide at 266 nm and 213 nm and indirectly by the reaction of propene with Cl atoms, which were generated by photolysis from oxalyl chloride at 266 nm. Experiments were conducted at room temperature at low pressures between 0.8 and 3 mbar using Ar as the buffer gas and with excess O 2 to maintain nearly pseudo-first-order reaction conditions. Whereas allyl was detected by photoionisation using synchrotron radiation, the main reaction product allyl peroxy was not observed due to dissociative ionisation of this weakly bound species. From the concentration–time profiles of the allyl signal, second-order rate constants between 1.35 × 10 11 cm 3 mol −1 s −1 at 0.8 mbar and 1.75 × 10 11 cm 3 mol −1 s −1 at 3 mbar were determined. The rates obtained for the different allyl radical generation schemes agree well with each other, but are about a factor of 2 higher than the ones reported previously using He as a buffer gas. The discrepancy is partly attributed to the higher collision efficiency of Ar causing a varying fall-off behavior. When allyl is produced by the reaction of propene with Cl atom, an unexpected product is observed at m / z = 68, which was identified as 1,3-butadienal in the threshold photoelectron spectrum. It is formed in a secondary reaction of allyl with the OCCl radical, which is generated in the 266 nm photolysis of oxalyl chloride.
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- Award ID(s):
- 1665464
- PAR ID:
- 10066638
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 20
- Issue:
- 16
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 10721 to 10731
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c7cp07893e
