Binary Intermetallics in the 70 atom % R Region of Two R-Pd Systems (R = Tb and Er): Hidden, Obscured, or...

Although rare-earth-metal-transition-metal (R/T) phase diagrams have been explored extensively, our recent studies have uncovered new previously nonexistent binary intermetallics. These compounds belong to a narrow region between 70 and 71.4 atom % of the rare-earth metal but represent four different structure types. The binaries Tb₇Pd₃ and Er₁₇Pd₇ are compositionally approaching (less than 1 atom % difference) the previously reported R_2.16Pd_0.89 (R = Tb and Er), and apparently form by peritectoid transformation, thus, being hard to detect by fast cooling. Tb₇Pd₃ (1) crystallizes in the Th₇Fe₃ structure type (hP20, P6₃mc, a = 9.8846(4) Å, c = 6.2316(3) Å, Z = 2) while Er₁₇Pd₇ (2) belongs to the Pr₁₇Co₇ type being its second reported representative (cP96, P2₁3, a = 13.365(2) Å, Z = 4). Er₁₇Pd₇ (2) is overlapping with the cubic F-centered Er_2.11Pd_0.89 (3b, Fd3̅m, a = 13.361(1) Å, Z = 32) with practically identical unit cell parameters but a significantly different structure. Electronic structure calculations confirm that heteroatomic R-T bonding strongly dominates in all structures; T-T bonding interactions are individually strong but do not play a significant role in the total bonding.