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Final State Resolved Quantum Predissociation Dynamics of SO 2 (C̃ 1 B 2 ) and Its Isotopomers via a Crossing with a Singlet Repulsive State.
Journal of Physical Chemistry. A 2017 July 7
The fragmentation dynamics of predissociative SO2 (C̃1 B2 ) is investigated on an accurate adiabatic potential energy surface (PES) determined from high level ab initio data. This singlet PES features non-C2v equilibrium geometries for SO2 , which are separated from the SO(X̃3 Σ- ) + O(3 P) dissociation limit by a barrier resulting from a conical intersection with a repulsive singlet state. The ro-vibrational state distribution of the SO fragment is determined quantum mechanically for many predissociative states of several sulfur isotopomers of SO2 . Significant rotational and vibrational excitations are found in the SO fragment. It is shown that these fragment internal state distributions are strongly dependent on the predissociative vibronic states, and the excitation typically increases with the photon energy.
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