Ultraviolet Photodissociation Dynamics of the Allyl Radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) Electronic Excited States

The Journal of Physical Chemistry. a
Yu SongChristopher Brazier

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 isotr...Continue Reading

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Citations

Mar 11, 2016·The Journal of Physical Chemistry. a·Michael LucasJoel M Bowman
Feb 2, 2017·Annual Review of Physical Chemistry·Michael N R AshfoldThomas A A Oliver
Jan 24, 2019·Physical Chemistry Chemical Physics : PCCP·Michael N R AshfoldJingsong Zhang
Mar 4, 2020·Physical Chemistry Chemical Physics : PCCP·Marta G GonzálezLuis Bañares
Sep 9, 2018·The Journal of Chemical Physics·Michael N R AshfoldXueming Yang
Sep 3, 2017·The Journal of Chemical Physics·Kai PachnerIngo Fischer
Jun 17, 2021·The Journal of Physical Chemistry. a·Michael LucasJingsong Zhang
Oct 31, 2019·The Journal of Physical Chemistry. a·Ge SunJoel M Bowman
Oct 6, 2021·The Journal of Physical Chemistry. a·Ge SunJingsong Zhang

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