Electronic band structure and optical properties of the cubic Sc, Y and La hybride systems

Electronic band structure calculations are used to interpret the optical spectra of the cubic Sc, Y and La hydride systems. Self-consistent band calculations of ScH(,2) and YH(,2) are carried out using the Korringa-Kohn-Rostoker method. The respective joint densities of states are computed and compared to the dielectric functions determined from the optical measurements of Weaver, Rosei and Peterson. Additional calculations are performed in which the Fermi level or band gap energies are rigidly shifted by a small energy increment. These calculations are then used to simulate the derivative structure in thermomodulation spectra and relate the origin of experimental interband features to the calculated energy bands. While good systematic agreement is obtained for several spectral features, the origin of low-energy interband transitions in YH(,2) cannot be explained by these calculated bands. A lattice-size-dependent premature occupation of octahedral sites by hydrogen atoms in the fcc metal lattice is suggested to account for this discrepancy. Various non-self-consistent calculations are used to examine the effect of such a premature occupation. Measurements of the optical absorptivity of LaH(,x) with 1.6 \u3c x \u3c 2.9 are presented which, as expected, indicate a more premature occupation of the octahedral sites in the larger LaH(,2) lattice. These experimental results also suggest that, in contrast to recent calculations, LaH(,3) is a small-band-gap semiconductor;*DOE Report IS-T-899. This work was performed under Contract W-7405-eng-82 with the Department of Energy