Correlation between band structure and hydride formation in dilute palladium alloys

Data on the free energy change ΔG, following solution of hydrogen in dilute Pd-alloys Pd_1?xM_x have been reviewed for different concentrations of M (M = Au, Ag, Pt, Ir, Rh, V, Cu, Ni, Pb, Sn and Ti) in both the α and β phases. The dependence of ΔG values upon the nature of the substituents (transition metals) is consistently explained within the framework of a metal-hydrogen bonding mechanism in the hydrides. For the β-hydride the ΔG values can be calculated on the basis of the equation ΔG = ΔG_pd + a(T)(〈?^M_LB〉 ? 〈?^Pd_LB〉)x, where $\text{ΔG}{}_{\mathrm{<mtext>Pd</mtext>}}\text{= ? 0.0489}\text{eV}\text{H}$ atom and is the free energy change of solution of hydrogen in pure Pd, a(T) = 0.194 at T = 298 K, 〈?^m_LB〉 and 〈?^pd_LB〉 are the average energies of the lowest band of the pure constituents ($\text{〈?}{}^{\mathrm{<mtext>Pd</mtext>}}{}_{\mathrm{<mtext>LB</mtext>}}\text{〉 = ?9.15}\text{eV}\text{atom}$). The stability of the palladium-hydrogen bond in dilute Pd-alloys depends on the value of 〈?^M_LB〉; for substituents having lower 〈?^M_LB〉 values than Pd the bond will strengthen, while for those having higher 〈?^M_LB〉 values it will weaken. This behaviour agrees well with the general trend of the stability of the stoichiometric hydrides predicted by Gelatt, Ehrenreich and Weiss using band structure results.