CF3NO photodissociation dynamics

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Abstract
The predissociation of CF3NO from 600–680 nm has been studied by monitoring the nascent NO product in real time using a two-photon laser excited fluorescence (TPEF) technique. The observation that the rate of production of NO is equal to the rate of decay of excited CF3NO indicates that no long-lived intermediate is involved in the dissociation. Detection of NO(v″=3) following 600 nm dissociation sets an upper limit of 33 kcal/mole on the C–N bond dissociation energy. The nascent vibrational and rotational distributions estimated from the observed TPEF spectra establish that greater than 95% of the NO product is formed in its ground vibrational state and that all vibrational states are rotationally excited. The rotational excitation is discussed in terms of the dynamics of the dissociation. Possible predissociation mechanisms are considered.