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• W2419289915 endingPage "12328" @default.
• W2419289915 startingPage "12318" @default.
• W2419289915 abstract "Ultraviolet (UV) photodissociation dynamics of jet-cooled allyl radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) electronically excited states are studied at the photolysis wavelengths from 249 to 216 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The photofragment yield (PFY) spectra of the H atom products are measured using both allyl chloride and 1,5-hexadiene as precursors of the allyl radical and show a broad peak centered near 228 nm, whereas the previous UV absorption spectra of the allyl radical peak around 222 nm. This difference suggests that, in addition to the H + C3H4 product channel, another dissociation channel (likely CH3 + C2H2) becomes significant with increasing excitation energy. The product translational energy release of the H + C3H4 products is modest, with the P(ET) distributions peaking near 8.5 kcal/mol and the fraction of the average translational energy in the total excess energy, ⟨fT⟩, in the range 0.22-0.18 from 249 to 216 nm. The P(ET)'s are consistent with production of H + allene and H + propyne, as suggested by previous experimental and theoretical studies. The angular distributions of the H atom products are isotropic, with the anisotropy parameter β ≈ 0. The H atom dissociation rate constant from the pump-probe study gives a lower limit of 1 × 10(8)/s. The dissociation mechanism is consistent with unimolecular decomposition of the hot allyl radical on the ground electronic state after internal conversion of the electronically excited state." @default.
• W2419289915 created "2016-06-24" @default.
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• W2419289915 date "2015-09-11" @default.
• W2419289915 modified "2023-10-03" @default.
• W2419289915 title "Ultraviolet Photodissociation Dynamics of the Allyl Radical via the B̃²A₁(3s), C̃²B₂(3p_<i>y</i>), and Ẽ²B₁(3p_<i>x</i>) Electronic Excited States" @default.
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• W2419289915 doi "https://doi.org/10.1021/acs.jpca.5b06684" @default.
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• W2419289915 hasPublicationYear "2015" @default.
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