Threshold photoelectron spectroscopy of dichlorodifluoromethane (CF2Cl2) has been re-investigated using a combination of photoelectron-photoion coincidence measurement and density functional theory calculations. For the D2B2 band of threshold photoionization spectra in the energy range of 13.9–15.1 eV, a series vibrational peaks were clearly observed. Using the optimized geometries and vibrational frequencies of the CF2Cl2 neutral and its cations in the D2B2 ionic state at the M06-2X/aug-cc-pVTZ level of theory, Franck-Condon factor simulations were carried out, and showed perfect agreement with the experimental spectra. Accordingly, the satisfactory vibrational assignments for the D2B2 band were achieved, and the adiabatic and vertical ionization energies to the D2B2 ionic state were determined as 14.125±0.005 eV and 14.355±0.005 eV, respectively. Moreover, vibrational frequencies of the v1+ and v3+ modes were 1178 cm−1 and 361 cm−1, respectively, as well as the anharmonic parameter for the v3+ mode of 3.42 cm−1.

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