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At equilibrium and fixed island area, the relevant anisotropic step free energies, their atom coordination and any important strain determine shape through a two-dimensional Wulff construction. Since the island and substrate are the same element, lattice mismatch is not the main distinction here. Kinetic growth can change shape if equilibration is incomplete.

The two alternating step families on an fcc(111) surface have locally $\{100\}$-like and $\{111\}$-like microfacets. Nearly equal energies on Cu(111) favor approximately hexagonal islands. A sufficiently large difference on Pt(111) favors a truncated triangle or, in the strong-anisotropy limit, a triangle bounded by the lower-energy family.

With the hollow-site registration shown, the steps facing direction $\mathbf{b}$ are the more close-packed $\{111\}$-type steps and are expected to be lower in energy than the $\{100\}$-type steps facing $\mathbf{a}$. Their bonding and relaxation differ even though the upper terrace is the same close-packed lattice. Exact energy ratios or triangle truncations are not fixed by the diagram alone.

The Winterbottom construction extends the Wulff construction to a crystal supported on a substrate. It includes the particle-substrate interfacial energy and the substrate surface energy displaced by contact, so the equilibrium Wulff body is truncated by the support plane. The relevant contact contribution is $({\gamma }_{ps}-{\gamma }_s)A_{\mathrm{contact}}$; it determines wetting and contact geometry. The basic unsupported construction accounts only for orientation-dependent free surface energies.^[ref]

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.

A faceted, approximately equiaxed crystal is indicated. A truncated octahedron bounded by low-energy $\{111\}$ and $\{100\}$ facets is a plausible three-dimensional shape for an fcc metal particle; the hexagonal section alone does not uniquely distinguish it from other faceted polyhedra.

The Wulff construction minimizes ${\sum }_i{\gamma }_i{A}_i$ at fixed particle volume. Place a plane with normal ${\hat{\mathbf{n}}}_i$ a distance $h_i=C{\gamma }_i$ from a common centre and take the inner envelope. Low-surface-energy orientations survive as large facets. Annealing permits diffusion toward this equilibrium morphology, provided the time is sufficient. For a supported or strained alloy, substrate adhesion and elastic energy modify this simple free-particle construction.

The competition between crystallization, exposed surfaces, adhesion and elastic strain can be summarized byHere $\Delta g>0$ measures the bulk driving force from supersaturation, and the $\gamma$ values are interfacial free energies. For a free spherical nucleus, $\Delta G=4\pi r^2\gamma -4\pi r^3\Delta g/3$ gives $r_{\ast }=2\gamma /\Delta g$. A support changes the heterogeneous nucleation barrier through adhesion and geometry.

Precursor activities and supply rate, temperature, time, solvent and ligands control nucleation, attachment, detachment and surface diffusion. Many nuclei divide a fixed solute inventory into smaller particles; continued growth or Ostwald ripening can enlarge them. Substrate defects determine preferred nucleation sites; lattice mismatch and interface bonding constrain orientation and elastic relaxation. Facet-selective adsorption can change both surface energies and growth rates.

Near equilibrium, a free nanocrystal follows a Wulff construction; a supported particle can follow a Winterbottom construction. Under kinetic control, slowly advancing facets remain visible while rapidly growing ones disappear. Equilibrium facet energy and kinetic growth rate are different controls, so a crystal structure does not uniquely determine particle shape.

Three suitable examples are cubes bounded mainly by $\{100\}$ facets, octahedra bounded by $\{111\}$ facets, and truncated octahedra bounded by both $\{111\}$ and $\{100\}$ facets. These are crystallographically distinct shapes rather than three arbitrary rounded particle outlines.

At fixed volume the thermodynamic equilibrium shape minimizes $G_{\mathrm{surf}}={\sum }_i{\gamma }_i{A}_i$, with an edge/corner correction when particles are very small. In the Wulff construction, facet support-plane distances scale as their interfacial free energies. Silver's clean low-index energies, selective adsorption of ligands or ions, solvent chemical potential and possible support contact alter those energies. Crystal twinning and elastic strain can add further costs or stabilize multiply twinned forms. A face with slow attachment kinetics can also survive during growth even when that morphology is not the thermodynamic equilibrium Wulff shape. Homogeneous nucleation describes where nuclei form; it does not guarantee an thermodynamic equilibrium final shape.

The thermodynamic questions can be organized from precursor chemistry to the final supported shape:

Adsorbed ligands and solvent can change different facet energies by different amounts, so the relevant energies belong to the actual chemical environment. Small particles have large surface-to-volume ratios and are particularly sensitive to these terms.

This sequence identifies thermodynamic factors rather than guaranteeing that an equilibrium shape is reached. Facet-specific attachment rates, precursor delivery and limited annealing can preserve a kinetically selected shape even when another shape has lower free energy.

An equilibrium construction for a supported particle that modifies the Wulff construction using particle-support and support-medium interfacial energies. The support truncates the corresponding free-particle shape.