Paths to Stabilizing Electronically Aberrant Compounds: A Defect-Stabilized Polymorph and Constrained Atomic Motion in PtGa2

Abstract

The structures and properties of intermetallic phases are intimately connected to electron count; unfavorable electron counts can result in structural rearrangements or new electrical or magnetic behavior when no such transformation is available. The compound PtGa2 appears to teeter on the border between these two scenarios with its two polymorphs: a cubic fluorite type form (c-PtGa2) and a complex tetragonal superstructure (t-PtGa2) whose Pt-Pt connectivity aligns with the 18- n electron counting rule. Here, we investigate the factors underlying this polymorphism. Electronic structure calculations show that the transition to t-PtGa2 opens a pseudogap at the Fermi energy that can be traced to Pt-Pt isolobal bond formation, in line with the 18- n bonding scheme. Conversely, DFT-chemical pressure (CP) analysis reveals a network of positive local pressures along Pt-Ga contacts, requiring that the c-PtGa2 to t-PtGa2 transition follows tightly concerted atomic motions. Experimentally, a series of samples with varying Pt:Ga ratios were synthesized to examine the stability ranges of the polymorphs. Ga-poor samples yield exclusively the cubic polymorph over the full range of temperatures studied, which can be correlated to the enhanced incorporation of interstitial Pt atoms (at points of negative pressure in the CP scheme). At more Ga-rich compositions, however, t-PtGa2 emerges as a low-temperature form. In these samples, the t-PtGa2 to c-PtGa2 transition is found to be reversible, but with a large hysteresis that in single crystals can exceed 100 °C. Together, the theoretical and experimental results indicate that the c-PtGa2 phase is buttressed at its unfavorable electron count by the interstitial atoms and networks of positive CPs that restrict atomic motion, suggesting more general strategies for achieving exotic electronic structures in intermetallic materials.