Bond-order bond energy model for alloys

Abstract We introduce a novel way to parameterize alloy energies in the form of a bond-order bond energy model. There, a bond order function models the transition between competing phases and switches their respective bond energies on and off. For the case of the Ni-Cr-Mo alloys investigated here, which assume face- or body-centered cubic structures, we propose a sigmoidal switching function fitted to the c/a ratio of “Bain-like” cells. With that, the model does an excellent job in describing the DFT-calculated alloy energies. We also show that the average atomic charge density can vary considerably as a function of composition, which can significantly modify alloy bond energies from simple expectation. The fitted bond energies can among others be used to determine phase diagrams, where we find excellent agreement with previous assessments in the solid range for Ni-Cr and Cr-Mo phase diagrams once the necessary entropy terms are added. They also allow quantitative, composition-dependent calculation of chemical potentials, which we use to determine vacancy formation energies in binary NiCr alloys for configurations that have been energy-minimized with Monte Carlo simulations. We show that the resulting regime of negative formation energies is a sign for thermodynamic instability of the underlying crystal and lies in the two-phase concentration range in the phase diagram, resulting in a holistic picture that unites defect and phase stability through the fully quantitative link between stoichiometry and chemical potentials enabled by the proposed bond energy model.