Experimental and theoretical study on generalized oscillator strengths of the valence-shell electronic excitations in CF₄

We report an angle-resolved electron energy loss spectroscopy (EELS) study on the valence-shell electronic excitations in CF₄. Experimentally momentum-transfer-dependent generalized oscillator strengths (GOSs) or GOS profiles for low-lying electronic excitations at 12.6, 13.8, and 14.8 eV are derived from EELS spectra measured at an incident electron energy of 3 keV. We also calculate GOS profiles using theoretical wave functions at the equation-of-motion coupled cluster singles and doubles level. There are good agreements between experiment and theory except for a significant discrepancy at small momentum transfer for the 1t_l → 3s Rydberg excitation at 12.6 eV. The experimental GOS profile for 1t_l → 3s exhibits a shape that is typical of a dipole allowed transition, while the excitation is formally dipole forbidden. This symmetry breaking behavior is rationally accounted for by qualitatively analyzing the nature of vibronic coupling effects. For the excitation band at 13.8 eV, a shoulder and extrema are observed in the GOS profile and are then found to be mainly due to the 2 ¹T₂ transition. Furthermore, the theoretical GOS profile for the 2¹T₂ transition exhibits a remarkable oscillatory pattern; its origin is discussed by considering multicenter interference effects. For the 14.8 eV excitation band, the predominant nondipole nature of the underlying transitions are revealed and comparisons with the theoretical calculations show that major contributions to this band come from the 4t ₂ → 3p excitation.