We report a detailed augmented-plane-wave energy-band study and wave-function analysis of stoichiometric PdH which shows that, even though the Fermi surface of PdH is qualitatively similar to that of silver, the simple "proton model" is not valid. Instead, the screening of the proton in PdH is found to be larger than in an isolated H atom due, in part, to the formation of a H-Pd bonding band below the bottom of the d-band complex. This result, which is in qualitative agreement with Switendick's earlier calculation, is confirmed by ultraviolet photoemission experiments. A partial density-of-states (DOS) analysis in the energy range spanned by the six valence and conduction bands reveals the quantitative details of the bonding mechanism between the Pd and H constituents. At the Fermi energy, the high Pd d to H s DOS ratio 10.3 is found to be far higher than expected in silver, despite the fact that the Fermi-surface geometry is similar. The field-induced conduction-electron spin density at the proton site is evaluated from the wave functions at the Fermi energy. The calculated value of the spin-lattice relaxation rate arising from the contact term in the hyperfine interaction is found to be in good agreement with the experimental value of Wiley et al.
ASJC Scopus subject areas
- Condensed Matter Physics