MS-Xα calculation of the elastic electron scattering cross sections and x-ray absorption spectra of CX4 and SiX4 (X=H,F,Cl)

Abstract

Multiple scattering Xα bound state and continuum calculations are used to study low energy elastic electron scattering cross sections and pre-edge features in the x-ray absorption spectra (XAS) of (C,Si)X4, X=H,F,Cl. Maxima in the electron scattering cross section are predicted to occur at energies below 4 eV in the t2 channel for CF4, CCl4, SiH4, and SiCl4. These maxima can be assigned to final state orbitals which are bound in XAS and well localized in space and a quantitative correspondence of such scattering ‘‘resonance’’ energies and XAS energies may be obtained using the transition state approach. For CH4 and SiF4 even those bound state orbitals giving the greatest XAS intensity are very diffuse, being essentially of Rydberg character. Broad electron scattering maxima are found at energies above 4 eV in these molecules which cannot be directly associated with the bound state orbitals dominating the XAS. The results thus establish that low energy electron scattering resonances and pre-edge XAS are closely related only for orbitals bound and reasonably well localized in XAS. The MS-Xα results almost always reproduce experimental trends along the molecular series but quantitative discrepancies from experiment are sometimes substantial, particularly for the broad high energy scattering maxima in CH4. The narrow t2 resonance calculated for CF4 is found to vary greatly in position and intensity as the C–F distance is varied by small amounts but the stronger, broader t2 resonance in SiH4 is little affected by bond distance variation.