Abstract
The dissociation dynamics of the methoxy radical (CH 3O) following excitation of the A ( 2 A 1) ← X ( 2 E) transition are examined using photofragment translational spectroscopy. The radicals are produced from photodetachement of a fast, cold negative ion beam. We find that levels of the Ā state are strongly predissociated starting with ν 3 = 6 at 35419 cm −1 excitation energy. Three product channels are identified: (1) CH 3 + O, (2) CH 2 + OH, and (3) CH 2O + H, with channel (1) by far the dominant channel. In channel (1), resolved vibrational structure of the methyl fragment is seen in the translational energy distribution, providing insight into the dissociation dynamics of CH 3 O. Several thermodynamics quantities are also obtained: D 0(CH 3O) = 87.8 ± 0.3 kcal/mol, ΔH f,0 0(CH 3O) = 6.8 ± 0.4, D 0(CH 3OH) = 104.0 ± 0.5, ΔH acid,0(CH 3OH) = 381.4 ± 0.7, and D 0(HCH 2O) = 19.8 ± 0.4.
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