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A bulk fcc atom has twelve nearest neighbours, whereas surface atoms are undercoordinated: ideal (111) terrace atoms have nine and (100) terrace atoms eight. Steps, kinks, edges and corners can have still lower coordination and different bond-angle environments. These sites change electronic structure, adsorption energies and activation barriers, making geometrically different sites catalytically inequivalent.

In a Pt-Pd particle, a site's neighbours may be Pt, Pd or a mixture; surface segregation means surface composition need not equal overall composition. Alloying also changes strain and electronic interactions. Surface relaxation, reconstruction, adsorbed ligands, oxide or contamination can further alter accessibility and chemical state. A high nominal Pt fraction therefore does not establish either accessible Pt sites or a particular catalytic activity.

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.

Both starting arrangements converge toward the same chemically ordered alloy, exhibiting chemical ordering in alloys. This supports a lower free energy for the ordered unlike-metal neighbour pattern than for the segregated core-shell or disordered precursor at the final temperature. In a simple nearest-neighbour model, ordering is favoured whenwith consistent bond-energy conventions. Bulk mixing and ordering then compensate the loss of configurational entropy on cooling. Annealing alone does not supply numerical bond or surface energies, and elastic mismatch or adsorbed ligands can also matter.

The final morphology does not show a thick single-metal skin: the surface-energy difference is not large enough to overwhelm the bulk preference for ordering throughout the particle. Some atomic-scale surface enrichment is compatible with the drawing, so exact equality of the two surface free energies is not established.

If B has a much lower surface free energy, Surface segregation of B and an A-rich interior become favourable. A nearly continuous B shell is likely if enough B is present and the surface-energy gain exceeds the cost of disrupting favourable A-B bonds; otherwise only partial enrichment occurs.