Electronic excitations of fluoroethylenes

Abstract

Several lowest-lying singlet electronic states of vinyl fluoride, trans-, cis-, and 1,1-difluoroethylene, trifluoroethylene, and tetrafluoroethylene were investigated by using symmetry-adapted cluster configuration interaction theory. Basis sets up to Dunning's aug-cc-pVTZ augmented with appropriate Rydberg functions were utilized for the calculations. Calculated excitation energies show a good agreement with the available experimental values. Even in the troublesome pi-->pi(*) transitions, the excitation energies obtained in the present study agree well with the experimental values except in one or two fluoroethylenes. Strong mixing between different states was noticed in a few fluoroethylenes; especially the mixing is very strong between pi-pi(*) and pi-3ppi states in trifluoroethylene. No pure pi-sigma(*) excited state was found in almost all the fluoroethylenes. Several assignments and reassignments of features in the experimental spectra were suggested. The present study does not support the existing argument that the interaction between the pi-pi(*) and sigma-sigma(*) states is the reason behind the blueshift of around 1.25 eV in the pi-pi(*) excitation energy of tetrafluoroethylene. Possible reasons, including structural changes, for this shift are discussed in detail. Several low-lying triplet excited states were also studied.