Analysis of band broadening in vibrational high-resolution electron-energy-loss spectra of condensed methane

High-resolution vibrational electron-energy-loss spectra of multilayer condensed films of methane recorded at 20K show a strong tailing of the vibrational bands that clearly exceeds the instrumental resolution. At low incident electron energy, this tailing is remarkably less important for the dipole-allowed bending vibration (ν4) than for other bands. Also, the tailing becomes less pronounced with increasing size of the molecule as demonstrated by spectra of ethane and heptane recorded under the same conditions. Dipole coupling, rotational broadening, and multiple inelastic scattering have been considered as origins of this band broadening. While the first two effects can be excluded, multiple scattering involving a low-frequency phonon band provides a reasonable explanation as demonstrated by simulations of the spectrum of methane using a classical two-stream model. A lower phonon frequency in the cases of the larger molecules is held responsible for the better resolved vibrational signals in the spectra...