The vertical absorption spectrum and photodissociation mechanism of vinyl chloride (VC) were studied by using symmetry-adapted cluster configuration interaction theory. The important vertical ππ* excitation was intensively examined with various basis sets up to aug-cc-pVTZ augmented with appropriate Rydberg functions. The excitation energy for ππ* transition obtained in the present study, 6.96eV, agrees well with the experimental value, 6.76.9eV. Calculated excitation energies along with the oscillator strengths clarify that the main excitation in VC is the ππ* excitation. Contrary to the earlier theoretical reports, the results obtained here support that the C–Cl bond dissociation takes place through the nCl-σCCl* state.

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