A joint
experimental and theoretical investigation of the valence
shell excitations of carbon tetrachloride has been performed by fast
electron scattering and time dependent density functional theory calculations.
At a collision energy of 1.5 keV and an energy resolution of about
70 meV, the dipole-forbidden transition of a1σ* ←
2t1 has been clearly observed at large momentum transfers,
and its excitation energy of 6.15 eV and line width of 0.72 eV have
been determined. Two new features are also recognized at 9.97 and
10.26 eV. The generalized oscillator strengths of the excited states
at 5–11.3 eV have been determined from the measured spectra.
The calculated generalized oscillator strength of the a1σ* ← 2t1 transition with the vibronic effect
shows better agreement with the experiment, and the vibronic effect
also accounts for its nonzero intensity at zero squared momentum transfer.
The optical oscillator strengths of the valence shell excitations
have also been obtained by extrapolating the generalized oscillator
strengths to the limit of zero squared momentum transfer. The integral
cross sections have been systematically determined from the threshold
to 5000 eV by means of the BE-scaling method. The present oscillator
strengths and cross sections provide the fundamental data of carbon
tetrachloride and have important applications in photochemical modeling
for atmospheric physics.