Electronic spectra and photodissociation of vinyl chloride: a symmetry-adapted cluster configuration interaction study

Abstract

The vertical absorptionspectrum and photodissociation mechanism of vinyl chloride (VC) were studied by using symmetry-adapted cluster configuration interaction theory. The important vertical π→π* excitation was intensively examined with various basis sets up to aug-cc-pVTZ augmented with appropriate Rydberg functions. The excitation energy for π→π* transition obtained in the present study, 6.96eV, agrees well with the experimental value, 6.7–6.9eV. Calculated excitation energies along with the oscillator strengths clarify that the main excitation in VC is the π→π* excitation. Contrary to the earlier theoretical reports, the results obtained here support that the C–Cl bonddissociation takes place through the nCl-σ*C–Cl state. Show more