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• W2064694251 abstract "The dynamics of photodissociation of acetoxime at 193nm, leading to the formation of (CH3)2CN and OH fragments, has been investigated. The nascent OH radicals, which are both rotationally and vibrationally excited, were probed by laser photolysis–laser induced fluorescence technique. OH fragments in both v″=1 and v″=0 vibrational states were detected with a ratio of population in the higher to lower level of 0.07±0.01. The rotational temperatures of v″=0 and 1 levels of OH radicals are 2650±150K and 1290±20K, respectively. More than 30% of the available energy, i.e., 115±21kJmol−1 is partitioned into the relative translational energy of the fragments. The results of excited electronic state and transition state calculations at the configuration interaction with single electronic excitation level suggest that the dissociation takes place with an exit barrier of ∼126kJmol−1 at the triplet state (T2) potential energy surface, formed by internal conversions/intersystem crossing from the initially populated S2 state. Using the calculated transition state geometry and its energy, the observed energy distribution pattern can be reproduced by the hybrid model within experimental uncertainties. The presence of an exit barrier is further supported by the observation of N–OH dissociation upon 248nm excitation, where the relative translational energy of the fragments is found to be ∼96kJmol−1. The photodissociation dynamics of acetoxime is compared with C–OH dissociation in enols and carboxylic acid and N–OH dissociation in nitrous acid. The observed emission (λmax=430nm) and the N–OH dissociation dynamics indicate crossing of the initially populated state to an emissive state of acetoxime, which is different from the dissociative state." @default.
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• W2064694251 date "2005-05-08" @default.
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• W2064694251 title "Photodissociation dynamics of acetoxime in gas phase" @default.
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• W2064694251 doi "https://doi.org/10.1063/1.1897369" @default.
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