Toward Predicting the Assembly of Modular Intermetallics from Chemical Pressure Analysis: The Interface Nucleus Approach.

Complex intermetallic phases are often constructed from domains derived from simpler structures arranged into hierarchical assemblies. These modular arrangements offer intriguing prospects, such as the integration of the properties of distinct compounds into a single material or for the emergence of new properties from the interactions among different domains. In this article, we develop a strategy for the design of such complex structures, which we term the interface nucleus approach. Within this framework, the assembly of complex structures is facilitated by : geometrical motifs shared by two parent structures that serve as a region of overlap to nucleate or seed the formation of a combined structure. Our central hypothesis is that the formation of an interface between structures at these motifs creates opportunities for the relief of atomic packing stresses, as revealed by Density Functional Theory-Chemical Pressure (DFT-CP) analysis: when corresponding interatomic contacts in two structures exhibit complementarity─negative CP with positive CP or intense CP with mild CP─the intergrowth allows for a more balanced packing arrangement. To illustrate the application of the interface nucleus concept, we analyze three modular intermetallic structures, the σ-phase (FeCr), PuNi, and CaCuAl types. In each case, the assembly of the structure can be connected to complementary CP features in an interface nucleus shared by its parent structures, while the distribution of the interface nuclei in the parents serves to template the geometry of the overall framework. In this way, the interface nucleus approach points toward avenues for the design of modular intermetallics from the CP schemes of potential partner structures.