 Solution

The Wulff construction minimizes total orientation-dependent surface free energy at fixed crystal volume:Planes at distances proportional to their surface energies bound the equilibrium shape. The construction is thermodynamic; observed growth rates need not select the same shape.

For a mixed-metal particle, minimize a more complete free energy including bulk mixing/ordering, Au–Ag interface energy, exposed-surface composition, adsorbates and elastic strain, while conserving the amount of each metal. Important parameters include orientation-dependent surface energies, metal chemical potentials, interface coherency, lattice mismatch, temperature and ligand coverage. surface segregation can change the exposed composition and hence the relevant ${\gamma }_i$.

A generalized free-energy minimization can address a multicomponent particle; the elementary Wulff construction alone does not predict its core-shell composition. Sequential Au-core formation and Ag deposition can preserve a kinetically trapped interface when diffusion is too slow to reach equilibrium. If shape relaxation is fast but interdiffusion slow, an external shape may approach a constrained minimum even though the complete particle is not at global equilibrium. Growth kinetics, ligand stabilization and finite-size effects limit a bare-surface equilibrium model. A faceted image is therefore insufficient proof that either shape or composition is an equilibrium state.