Transition from Icosahedral to Decahedral Structure in a Coexisting Solid-Liquid Nickel Cluster

We have used molecular dynamics simulations to construct a microcanonical caloric curve for a 1415-atom Ni icosahedron. Prior to melting the Ni cluster exhibits static solid-liquid phase coexistence. Initially a partial icosahedral structure coexists with a non-wetting melt. However at energies very close to the melting point the icosahedral structure is replaced by a truncated decahedral structure which is almost fully wet by the melt. This structure remains until the cluster fully melts. The transition appears to be driven by a preference for the melt to wet the decahedral structure.Comment: 7 pages, 6 figure

Structure prediction for multicomponent materials using biminima.

The potential energy surface of a heteroparticle system will contain points that are local minima in both coordinate space and permutation space for the different species. We introduce the term biminima to describe these special points, and we formulate a deterministic scheme for finding them. Our search algorithm generates a converging sequence of particle-identity swaps, each accompanied by a number of local geometry relaxations. For selected binary atomic clusters of size N = N(A) + N(B) ≤ 98, convergence to a biminimum on average takes 3 N(A)N(B) relaxations, and the number of biminima grows with the preference for mixing. The new framework unifies continuous and combinatorial optimization, providing a powerful tool for structure prediction and rational design of multicomponent materials.This work was nancially supported by EPSRC grant EP/J010847/1 and the ERC.This is the accepted manuscript. The final version's available from APS at http://journals.aps.org/prl/abstract/10.1103/PhysRevLett.113.156102

Communication: a new paradigm for structure prediction in multicomponent systems.

We analyse the combinatorial aspect of global optimisation for multicomponent systems, which involves searching for the optimal chemical ordering by permuting particles corresponding to different species. The overall composition is presumed fixed, and the geometry is relaxed after each permutation in order to relieve local strain. From ideas used to solve graph partitioning problems we devise a deterministic search scheme that outperforms (by orders of magnitude) conventional and self-guided basin-hopping global optimisation. The search is guided by the energy gain from either swapping particles i and j (ΔEij) or changing the identity of particles i (ΔEi). These quantities are derived from the underlying (arbitrary) energy function, hence not constituting external bias, and for site-separable force fields each ΔEi can be approximated simply and efficiently. In our self-guided variant of basin-hopping, particles are weighted by an approximate ΔEi when randomly selected for an exchange, yielding a significant improvement for segregated multicomponent systems with modest particle size mismatch.This work was nancially supported by the EPSRC grant EP/J010847/1.This is the accepted manuscript. The final version's available from AIP at http://scitation.aip.org/content/aip/journal/jcp/139/22/10.1063/1.4843956?track=twee

Solid-liquid phase coexistence and structural transitions in palladium clusters

We use molecular dynamics with an embedded atom potential to study the behavior of palladium nanoclusters near the melting point in the microcanonical ensemble. We see transitions from both fcc and decahedral ground state structures to icosahedral structures prior to melting over a range of cluster sizes. In all cases this transition occurs during solid-liquid phase coexistence and the mechanism for the transition appears to be fluctuations in the molten fraction of the cluster and subsequent recrystallization into the icosahedral structure.Comment: 8 pages, 6 figure

Grand and Semigrand Canonical Basin-Hopping.

We introduce grand and semigrand canonical global optimization approaches using basin-hopping with an acceptance criterion based on the local contribution of each potential energy minimum to the (semi)grand potential. The method is tested using local harmonic vibrational densities of states for atomic clusters as a function of temperature and chemical potential. The predicted global minima switch from dissociated states to clusters for larger values of the chemical potential and lower temperatures, in agreement with the predictions of a model fitted to heat capacity data for selected clusters. Semigrand canonical optimization allows us to identify particularly stable compositions in multicomponent nanoalloys as a function of increasing temperature, whereas the grand canonical potential can produce a useful survey of favorable structures as a byproduct of the global optimization search.FC acknowledges generous computational resources granted by the regional Pôle Scientifique de Modélisation Numérique in Lyon. DJW and DS acknowledge financial support from the EPSRC and the ERC.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.jctc.5b0096

Impurity effects on solid-solid transitions in atomic clusters

We use the harmonic superposition approach to examine how a single atom substitution affects low-temperature anomalies in the vibrational heat capacity (C$_{V}$) of model nanoclusters. Each anomaly is linked to competing solidlike "phases", where crossover of the corresponding free energies defines a solid-solid transition temperature (T$_{s}$). For selected Lennard-Jones clusters we show that T$_{s}$ and the corresponding CV peak can be tuned over a wide range by varying the relative atomic size and binding strength of the impurity, but excessive atom-size mismatch can destroy a transition and may produce another. In some tunable cases we find up to two additional C$_{V}$ peaks emerging below Ts, signalling one- or two-step delocalisation of the impurity within the ground-state geometry. Results for Ni$_{74}$X and Au$_{54}$X clusters (X = Au, Ag, Al, Cu, Ni, Pd, Pt, Pb), modelled by the many-body Gupta potential, further corroborate the possibility of tuning, engineering, and suppressing finite-system analogues of a solid-solid transition in nanoalloys.This work was funded by the ERC and EPSRC grant EP/J010847/1. BEH also acknowledges the Gates Cambridge Trust for financial support

Quasi-combinatorial energy landscapes for nanoalloy structure optimisation.

We formulate nanoalloy structure prediction as a mixed-variable optimisation problem, where the homotops can be associated with an effective, quasi-combinatorial energy landscape in permutation space. We survey this effective landscape for a representative set of binary systems modelled by the Gupta potential. In segregating systems with small lattice mismatch, we find that homotops have a relatively straightforward landscape with few local optima - a scenario well-suited for local (combinatorial) optimisation techniques that scale quadratically with system size. Combining these techniques with multiple local-neighbourhood structures yields a search for multiminima, and we demonstrate that generalised basin-hopping with a metropolis acceptance criterion in the space of multiminima can then be effective for global optimisation of binary and ternary nanoalloys.This work was financially supported by EPSRC Grant No. EP/J010847/1 and the ERC.This is the final version of the article. It first appeared from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5CP01198

Superheating and solid-liquid phase coexistence in nanoparticles with non-melting surfaces

We present a phenomenological model of melting in nanoparticles with facets that are only partially wet by their liquid phase. We show that in this model, as the solid nanoparticle seeks to avoid coexistence with the liquid, the microcanonical melting temperature can exceed the bulk melting point, and that the onset of coexistence is a first-order transition. We show that these results are consistent with molecular dynamics simulations of aluminum nanoparticles which remain solid above the bulk melting temperature.Comment: 8 pages, 5 figure

Structure, thermodynamics, and rearrangement mechanisms in gold clusters - Insights from the energy landscapes framework

We consider finite-size and temperature effects on the structure of model AuN clusters (30 ≤ N ≤ 147) bound by the Gupta potential. Equilibrium behaviour is examined in the harmonic superposition approximation, and the size-dependent melting temperature is also bracketed using molecular dynamics simulations. We identify structural transitions between distinctly different morphologies, characterised by various defect features. Reentrant behaviour and trends with respect to cluster size and temperature are discussed in detail. For N = 55, 85, and 147 we visualise the topography of the underlying potential energy landscape using disconnectivity graphs, colour-coded by the cluster morphology; and we use discrete path sampling to characterise the rearrangement mechanisms between competing structures separated by high energy barriers (up to 1 eV). The fastest transition pathways generally involve metastable states with multiple fivefold disclinations and/or a high degree of amorphisation, indicative of melting. For N = 55 we find that reoptimising low-lying minima using density functional theory (DFT) alters their energetic ordering and produces a new putative global minimum at the DFT level; however, the equilibrium structure predicted by the Gupta potential at room temperature is consistent with previous experiments.</p

Structure, thermodynamics, and rearrangement mechanisms in gold clusters-insights from the energy landscapes framework.

We consider finite-size and temperature effects on the structure of model AuN clusters (30 ≤ N ≤ 147) bound by the Gupta potential. Equilibrium behaviour is examined in the harmonic superposition approximation, and the size-dependent melting temperature is also bracketed using molecular dynamics simulations. We identify structural transitions between distinctly different morphologies, characterised by various defect features. Reentrant behaviour and trends with respect to cluster size and temperature are discussed in detail. For N = 55, 85, and 147 we visualise the topography of the underlying potential energy landscape using disconnectivity graphs, colour-coded by the cluster morphology; and we use discrete path sampling to characterise the rearrangement mechanisms between competing structures separated by high energy barriers (up to 1 eV). The fastest transition pathways generally involve metastable states with multiple fivefold disclinations and/or a high degree of amorphisation, indicative of melting. For N = 55 we find that reoptimising low-lying minima using density functional theory (DFT) alters their energetic ordering and produces a new putative global minimum at the DFT level; however, the equilibrium structure predicted by the Gupta potential at room temperature is consistent with previous experiments