Whereas the Daltonian atom-to-atom ratios in ordinary molecules are well understood via the traditional theory of valence, the naturally occurring stoichiometries in intermetallic compounds ${A}_{p}{B}_{q}$, as revealed by phase-diagram compilations, are often surprising. Even equal-valence elements $A$ and $B$ give rise to unequal $(p,q)$ stoichiometries, e.g., the 1:2, 2:1, and 3:1 ratios in ${\text{Al}}_{p}{\text{Sc}}_{q}$. Moreover, sometimes different stoichiometries are associated with different lattice types and hence rather different physical properties. Here, we extend the fixed-composition global space-group optimization (GSGO) approach used to predict, via density-functional calculations, fixed-composition lattice types [G. Trimarchi and A. Zunger, J. Phys.: Condens. Matter 20, 295212 (2008)] to identify simultaneously all the minimum-energy lattice types throughout the composition range. Starting from randomly selected lattice vectors, atomic positions and stoichiometries, we construct the $T=0$ ``convex hull'' of energy vs composition. Rather than repeat a set of GSGO searches over a fixed list of stoichiometries, we minimize the distance to the convex hull. This approach is far more efficient than the former one as a single evolutionary search sequence simultaneously identifies the lowest-energy structures at each composition and among these it selects those that are ground states. For Al-Sc we correctly identify the stable stoichiometries and relative structure types: ${\text{AlSc}}_{2}\text{-B}{8}_{2}$, AlSc-B2, and ${\text{Al}}_{2}\text{Sc-C}15$ in the ${N}_{at}=6$ periodic cells, and ${\text{Al}}_{2}{\text{Sc}}_{6}\text{-D}{0}_{19}$, AlSc-B2, and ${\text{Al}}_{3}\text{Sc-L}{1}_{0}$ in the ${N}_{at}=8$ periodic cells. This extended evolutionary GSGO algorithm represents a step toward a fully ab initio materials synthesis, where compounds are predicted starting from sole knowledge of the chemical species of the constituents.
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