We introduce terms, an open-source Fortran program to simulate near-field and far-field optical properties of clusters of particles. The program solves rigorously the Maxwell equations via the superposition T-matrix method, where incident and scattered fields are decomposed into series of vector spherical waves. terms implements several algorithms to solve the coupled system of multiple scattering equations that describes the electromagnetic interaction between neighbouring scatterers. From this formal solution, the program can compute a number of physically-relevant optical properties, such as far-field cross-sections for extinction, absorption, scattering and their corresponding circular dichroism, as well as local field intensities and degree of optical chirality. By describing the incident and scattered fields in a basis of spherical waves the T-matrix framework lends itself to analytical formulas for orientation-averaged quantities, corresponding to systems of particles in random orientation; terms offers such computations for both far-field and near-field quantities of interest. This user guide introduces the program, summarises the relevant theory, and is supplemented by a comprehensive suite of stand-alone examples in the website accompanying the code.

Incorporation of catalytically active materials into plasmonic metal nanostructures can efficiently merge the reactivity and energy harvesting abilities of both types of materials for visible light photocatalysis. Here we explore the influence of electromagnetic hotspots in the ability of plasmonic core-shell colloidal structures to induce chemical transformations. For this study, we developed a synthetic strategy for the fabrication of Au nanoparticle (NP) trimers in aqueous solution through fine controlled galvanic replacement between Ag nanoprisms and Au precursors. Core-shell Au@M NP trimers with catalytically active metals (M = Pd, Pt) were subsequently synthesized using Au NP trimers as templates. Our experimental and computational results highlight the synergy of geometry and composition in plasmonic catalysts for plasmon-driven chemical reactions.

Corner and edge sites have long been predicted to play a dominant role in the chemistry of nanomaterials due to their low metal-metal coordination numbers. However, due to the difficulty in directly observing chemical reactions, a detailed understanding of how a material's crystallographic sites and morphology affect those sites' reaction kinetics is limited. Using environmental scanning transmission electron microscopy (ESTEM), we report direct observations under continuous reaction conditions of site-dependent chemical reactivity critical to corrosion and heterogeneous catalysis. A range of fcc nickel nanocrystal morphologies bound by the low index {111} facets (triangular plates, hexagonal plates, and decahedral and icosahedral nanoparticles) were studied during oxidation to visualize in situ changes using atomic number (Z) contrast ESTEM. Oxidation is shown to occur preferentially at the corner sites and then the edges. The enhanced oxidation rate of the corners persists until corrosion has progressed to a depth of similar to 2-4 nm, depending on the nanoparticle geometry. The nanoparticle systems showed that the triangular plates were the most reactive followed by the hexagonal plates, decahedra, and icosahedra. Time-resolved measurements of oxidation rates show a size-dependent induction period for the edges, hypothesized to be due to oxygen diffusion along the surface of the smaller particles to react preferentially at the more reactive corner sites.

The T-matrix framework offers accurate and efficient modelling of electromagnetic scattering by nonspherical particles in a wide variety of applications ranging from nano-optics to atmospheric science. Its analytical setting, in contrast to purely numerical methods, also provides a fertile ground for further theoretical developments. Perhaps the main purported limitation of the method, when extended to systems of multiple particles, is the often-stated requirement that the smallest circumscribed spheres of neighbouring scatterers not overlap. We consider here such a scenario with two adjacent spheroids whose aspect ratio we vary to control the overlap of the smallest circumscribed spheres, and compute far-field cross-sections and near-field intensities using the superposition T-matrix method. The results correctly converge far beyond the no-overlap condition, and although numerical instabilities appear for the most extreme cases of overlap, requiring high multipole orders, convergence can still be obtained by switching to quadruple precision. Local fields converge wherever the Rayleigh hypothesis is valid for each single scatterer and, remarkably, even in parts of the overlap region. Our results are validated against finite-element calculations, and the agreement demonstrates that the superposition T-matrix method is more robust and broadly applicable than generally assumed.

© 2019 American Physical Society. In electromagnetic scattering, the so-called T matrix encompasses the optical response of a scatterer for any incident excitation and is most commonly defined using the basis of multipolar fields. It can therefore be viewed as a generalization of the concept of polarizability of the scatterer. We calculate here the series expansion of the T matrix for a spheroidal particle in the small-size, long-wavelength limit, up to third lowest order with respect to the size parameter, X, which we will define rigorously for a nonspherical particle. T is calculated from the standard extended boundary condition method with a linear system involving two infinite matrices P and Q, whose matrix elements are integrals on the particle surface. We show that the limiting form of the P and Q matrices, which is different in the special case of spheroid, ensures that this Taylor expansion can be obtained by considering only multipoles of order 3 or less (i.e., dipoles, quadrupoles, and octupoles). This allows us to obtain self-contained expressions for the Taylor expansion of T(X). The lowest order is O(X3) and equivalent to the quasistatic limit or Rayleigh approximation. Expressions to order O(X5) are obtained by Taylor expansion of the integrals in P and Q followed by matrix inversion. We then apply a radiative correction scheme, which makes the resulting expressions valid up to order O(X6). Orientation-averaged extinction, scattering, and absorption cross sections are then derived. All results are compared to the exact T-matrix predictions to confirm the validity of our expressions and assess their range of applicability. For a wavelength of 400 nm, the new approximation remains valid (within 1% error) up to particle dimensions of the order of 100-200 nm depending on the exact parameters (aspect ratio and material). These results provide a relatively simple and computationally friendly alternative to the standard T-matrix method for spheroidal particles smaller than the wavelength, in a size range much larger than for the commonly used Rayleigh approximation.

We use the energy landscapes framework to shed new light on the structural diversity of model AuN clusters (30 ≤ N ≤ 147), and we find optimal transition pathways connecting prominent morphologies.

We analyze the structure of model NiN and CuN clusters (N = 55, 147) supported on a variety of atomically smooth van der Waals surfaces. The global minima are mapped in the space of two parameters: (i) the laterally averaged surface stickiness, γ, which controls the macroscopic wetting angle, and (ii) the surface microstructure, which produces more subtle but important templating via epitaxial stresses. We find that adjusting the substrate lattice (even at constant γ) can favor different crystal plane orientations in the cluster, stabilize hexagonal close-packed order, or induce various defects, such as stacking faults, twin boundaries, and five-fold disclinations. Thermodynamic analysis reveals substrate-dependent solid-solid transitions in cluster morphology, with tunable transition temperature and sometimes exhibiting re-entrant behavior. These results shed new light on the extent to which a supporting surface can be used to influence the equilibrium behavior of nanoparticles.

We use the energy landscapes framework to shed new light on the structural diversity of model AuN clusters (30 ≤ N ≤ 147), and we find optimal transition pathways connecting prominent morphologies.

We use the harmonic superposition approach to examine how a single atom substitution affects low-temperature anomalies in the vibrational heat capacity (CV) of model nanoclusters. Each anomaly is linked to competing solidlike "phases", where crossover of the corresponding free energies defines a solid-solid transition temperature (Ts). For selected Lennard-Jones clusters we show that Ts 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 CV peaks emerging below Ts, signalling one- or two-step delocalisation of the impurity within the ground-state geometry. Results for Ni74X and Au54X 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.

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.

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.

One of the simplest microscopic models for a thermally driven first-order phase transition is an Ising-type lattice system with nearest-neighbour interactions, an external field, and a degeneracy parameter. The underlying lattice and the interaction coupling constant control the anisotropic energy of the phase boundary, the field strength represents the bulk latent heat, and the degeneracy quantifies the difference in communal entropy between the two phases. We simulate the (stochastic) evolution of this minimal model by applying rejection-free canonical and microcanonical Monte Carlo algorithms, and we obtain caloric curves and heat capacity plots for square (2D) and face-centred cubic (3D) lattices with periodic boundary conditions. Since the model admits precise adjustment of bulk latent heat and communal entropy, neither of which affect the interface properties, we are able to tune the crystal nucleation barriers at a fixed degree of undercooling and verify a dimension-dependent scaling expected from classical nucleation theory. We also analyse the equilibrium crystal-melt coexistence in the microcanonical ensemble, where we detect negative heat capacities and find that this phenomenon is more pronounced when the interface is the dominant contributor to the total entropy. The negative branch of the heat capacity appears smooth only when the equilibrium interface-area-to-volume ratio is not constant but varies smoothly with the excitation energy. Finally, we simulate microcanonical crystal nucleation and subsequent relaxation to an equilibrium Wulff shape, demonstrating the model's utility in tracking crystal-melt interfaces at the atomistic level.

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.

Following a simple thermodynamic model, which predicts that an array of non-wettable pores can be filled by dewetting of sufficiently thin films, we use molecular dynamics to simulate the rupture of nanometre-thick liquid Au films on nanoporous substrates. Our simulations clearly exhibit spinodal dewetting and hole nucleation, and some of the metal is indeed absorbed by non-wettable pores solely as a virtue of the Laplace pressure acting on dewetted droplets and rivulet-like structures. Finally, we show that the fraction of absorbed Au can be increased through patterning of the initial film.

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 aims to provide simple and accurate closed-form approximations to predict the scattering and absorption spectra of metallic nanospheres and nanoshells supporting localised surface plasmon resonances. Particular attention is given to the validity and accuracy of these expressions in the range of nanoparticle sizes relevant to plasmonics, typically limited to around 100 nm in diameter. Using recent results on the rigorous radiative correction of electrostatic solutions, we propose a new set of long-wavelength polarizability approximations for both nanospheres and nanoshells. The improvement offered by these expressions is demonstrated with direct comparisons to other approximations previously obtained in the literature, and their absolute accuracy is tested against the exact Mie theory.

The electronic structure of known cluster compounds with a cage-like icosahedral Ga-12 centre is studied by first-principles theoretical methods, based on density functional theory. We consider these hollow metalloid nanostructures in the context of the polymorphism of the bulk, and identify a close relation to the alpha phase of gallium. This previously unrecognised connection is established using the electron localisation function, which reveals the ubiquitous presence of radially-pointing covalent bonds around the Ga-12 centre - analogous to the covalent bonds between buckled deltahedral planes in alpha-Ga. Furthermore, we find prominent superatom shell structure in these clusters, despite their hollow icosahedral motif and the presence of covalent bonds. The exact nature of the electronic shell structure is contrasted with simple electron shell models based on jellium, and we demonstrate how the interplay between gallium dimerisation, ligand- and crystal-field effects can alter the splitting of the partially filled 1F shell. Finally, in the unique compound where the Ga-12 centre is bridged by six phosphorus ligands, the electronic structure most closely resembles that of delta-Ga and there are no well-defined superatom orbitals. The results of this comprehensive study bring new insights into the nature of chemical bonding in metalloid gallium compounds and the relation to bulk gallium metal, and they may also guide the development of more general models for ligand-protected clusters.

Motivated by experimental reports of higher-than-bulk melting temperatures in small gallium clusters, we perform first-principles molecular dynamics simulations of Ga(20) and Ga(20)(+) using parallel tempering in the microcanonical ensemble. The respective specific heat (C(V)) curves, obtained using the multiple histogram method, exhibit a broad peak centered at approximately 740 and 610 K--well above the melting temperature of bulk gallium (303 K) and in reasonable agreement with experimental data for Ga(20)(+). Assessment of atomic mobility confirms the transition from solid-like to liquid-like states near the C(V) peak temperature. Parallel tempering molecular dynamics simulations yield low-energy isomers that are ~0.1 eV lower in energy than previously reported ground state structures, indicative of an energy landscape with multiple, competing low-energy morphologies. Electronic structure analysis shows no evidence of covalent bonding, yet both the neutral and charged clusters exhibit greater-than-bulk melting temperatures.

We give an account of recent studies of droplet uptake and withdrawal from carbon nanotubes using simple theoretical arguments and molecular dynamics simulations. Firstly, the thermodynamics of droplet uptake and release is considered and tested via simulation. We show that the Laplace pressure acting on a droplet assists capillary uptake, allowing sufficiently small non-wetting droplets to be absorbed. We then demonstrate how the uptake and release of droplets of non-wetting fluids can be exploited for the use of carbon nanotubes as nanopipettes. Finally, we extend the Lucas-Washburn model to deal with the dynamics of droplet capillary uptake, and again test this by comparison with molecular dynamics simulations.