First principles analysis of hydrogen chemisorption on Pd-Re alloyed overlayers and alloyed surfaces

Gradient corrected periodic density functional theory (DFT-GGA) slab calculations were used to examine the chemisorption of atomic hydrogen on various Pd-Re alloyed overlayers and uniformly alloyed surfaces. Adsorption was examined at 33% surface coverage, where atomic hydrogen preferred the three-fold fee sites. The binding energy of atomic hydrogen is observed to vary by as much as 0.7 eV due to Pd-Re interactions. The computed adsorption energies were found to be between -2.35 eV [for monolayer Pd-on-Re, i.e., Pd_ML/Re(0001)] and -3.05 eV [for Pd₃₃ Re₆₆/Pd(111)]. A d-band weighting scheme was developed to extend the Hammer-Nørskov surface reactivity model [Surf. Sci. 343, 211 (1995)] to the analysis of bimetallic Pd-Re alloyed systems. The hydrogen chemisorption energies are correlated linearly to the surface d-band center, which is weighted appropriately by the d-band coupling matrix elements for Pd and Re. The farther the weighted d-band center is shifted below the Fermi energy, the weaker is the interaction of atomic hydrogen with the alloyed Pd-Re surface.