Nonlocal First-Principles Calculations in Cu-Au and Other Intermetallic Alloys

Cu-Au is the prototypical alloy system used to exemplify ordering and compound formation, and it serves as a testbed for all new alloy theory methods. Yet, despite the importance of this system, conventional density functional theory (DFT) calculations with semilocal approximations have two dramatic failures in describing the energies of this system: (1) DFT formation energies of the observed Cu3Au and CuAu compounds are nearly a factor of 2 smaller in magnitude than experimental values, and (2) DFT predicts incorrect ordered ground states ground states for Au-rich compositions. Here, we show how modern extensions of DFT based on nonlocal interactions can rectify both of these failures. Our corrections shed light on improving the theoretical predictions for alloy systems to determine accurate formation energies, order-disorder critical temperatures, phase diagrams, and high-throughput computations.