Evidence for stepwise dissociation dynamics in acetone at 248 and 193 nm

Simon W. North, David A. Blank, J. Daniel Gezelter, Cheryl A. Longfellow, Yuan T. Lee

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Abstract

The technique of molecular beam photofragment translational spectroscopy has been used to study the dissociation of acetone following S 1←S0 (248 nm) and S2←-S0 (193 nm) excitation. Excitation at 248 nm resulted in the production of CH 3 and CH3CO with 14.2 ± 1.0 kcal/mole on average of the available energy appearing as translation of the photofragments. Comparison of the measured 〈ET〉 with values reported at 266 nm suggest that the energy partitioning is dominated by the exit barrier caused by an avoided crossing on the potential energy surface. A substantial fraction (30± 4%) of the nascent acetyl radicals from the primary dissociation contain sufficient energy to undergo spontaneous secondary decomposition. From the onset of the truncation of the CH3CO P〈ET〉 a threshold of 17.8± 3.0 kcal/mole for the dissociation of the acetyl radical has been determined in agreement with recent results on the photodissociation of acetyl chloride. The translational energy release in the dissociation of CH3CO closely matches the experimentally determined exit barrier. At 193 nm the only observed dissociation pathway was the formation of two methyl radicals and carbon monoxide. On average ∼ 38% of the available energy is found in product translation suggesting that significant internal energy resides in the nascent CH3 fragments consistent with the results of Hall et al. [J. Chem. Phys. 94, 4182 (1991)]. We conclude that the dynamics and energy partitioning for dissociation at 193 nm is similar to that at 248 nm.

Original languageEnglish (US)
Pages (from-to)4447-4460
Number of pages14
JournalThe Journal of chemical physics
Volume102
Issue number11
DOIs
StatePublished - 1995

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