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• W1968586831 startingPage "7329" @default.
• W1968586831 abstract "Unimolecular decomposition rates for acetyl radical following the photodissociation of acetyl cyanide and acetic acid near 193 nm have been studied using ultrafast mass-resolved photoionization spectroscopy. In both cases, the parent decays with an instrumentally limited lifetime, while the acetyl radical behaves in a manner consistent with an RRKM mechanism, in contrast to our previous results on acetone. It is necessary to convolute the population distribution with the microcanonical RRKM rates in order to achieve this agreement. We have also undertaken an ab initio study of the excited states of acetyl cyanide to clarify the assignments of these states. The state excited at 193 nm arises from a π→π* transition with a calculated transition velocity dipole moment oriented at an angle of 57° with respect to the C–C≡N bond, resulting in an anisotropy parameter of −0.22. This is in reasonable agreement with the previous data of North et al. [J. Phys. Chem. A 101, 9224 (1997)]. The apparent RRKM behavior of the acetyl radical formed by the photodissociation of acetic acid and acetyl cyanide indicates that acetyl radical produced by the photodissociation of acetone at 193 nm may exhibit “extrinsic non-RRKM” effects, i.e., dynamic bottlenecks or mode specific effects." @default.
• W1968586831 created "2016-06-24" @default.
• W1968586831 creator A5042952880 @default.
• W1968586831 creator A5082346178 @default.
• W1968586831 date "1999-10-22" @default.
• W1968586831 modified "2023-10-17" @default.
• W1968586831 title "Ultrafast photodissociation studies of acetyl cyanide and acetic acid and unimolecular decomposition rates of the acetyl radical products" @default.
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• W1968586831 doi "https://doi.org/10.1063/1.480056" @default.
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