Journal of Chemical Physics p. 6615 - 6624 (1994)
Update date:2022-08-12
Topics:
Shin, S. K.
Jarek, R. L.
Boehmer, E.
Wittig, C.
Ethylene oxide, C2H4O, is a three-membered ring with a single oxygen atom bridging the two carbons.Reactions of H and D atoms with ethylene oxide have been studied in the gas phase to provide insight into the dynamics of three-membered ring opening.H atoms were produced by photolyzing HI in the wavelength range 240-266 nm.The channel leading to OH+C2H4 was monitored via laser-induced fluorescence (LIF) of the OH A 2Σ <- X 2Π system.The D atom reaction yields OD with no hydrogen scrambling.With an available energy of 23 000 cm-1, the average OH D rotational energy is ca. 350 cm-1 for OH(ν=0) and OD(ν=0) and ca. 250 cm-1 for OD(ν=1).OH(ν=1) was not observed, while the OD(ν=1) population was about one-tenth that of OD(ν=0).There was no apparent bias in populations between Λ doublets in each of the spin-orbit states for both OH and OD.Doppler broadening of OH(ν=0) rotational lines was measured to evaluate the average center-of-mass (c.m.) translational energy, which was found to be ca. 2300 cm-1.On average, the ring opening process deposits ca. 10percent of the available energy into c.m. translation, ca. 2percent into OH rotation, and ca. 88percent into ethylene internal energy.Comparison with CH2CH2OH unimolecular dissociation dynamics and theoretical transition state calculations leads to a likely mechanism in which hydrogen abstracts oxygen via sequential C-O bond fission without involving a long-lived CH2CH2OH intermediate.
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