Revisiting the CuPt 3 prototype and the L1 3 structure

Experimentally and computationally, the structure of Pt‐Cu at 1:3 stoichiometry has a convoluted history. The L1 3 structure has been predicted to occur in binary alloy systems, but has not been linked to experimental observations. Using a combination of electron diffraction, synchrotron X-ray powder diffraction, and Monte Carlo simulations, we demonstrate that it is present in the Cu‐Pt system at 1:3 stoichiometry. We also find that the 4-atom, fcc superstructure L1 3 is equivalent to the large 32-atom orthorhombic superstructure reported in older literature, resolving much of the confusion surrounding this composition. Quantitative Rietveld analysis of the X-ray data and qualitative trends in the electron-diffraction patterns reveal that the secondaryX þ ða;0;0Þorder parameter of the L1 3 phase is unexpectedly weak relative to the primaryL þ ða;a;0;0Þorder parameter, resulting in a partially-ordered L1 3 ordering, which we conclude to be the result of kinetic limitations. Monte Carlo simulations confirm the formation of a large cubic superstructure at high temperatures, and its eventual transformation to the L1 3 structure at lower temperature, but also provide evidence of other transitional orderings.