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Direct correlation functions (DCFs), linked to the second functional derivative of the free energy with respect to the one-particle density, play a fundamental role in a statistical mechanics description of matter. This holds in particular for the ordered phases: DCFs contain information about the local structure including defects and encode the thermodynamic properties of crystalline solids; they open a route to the elastic constants beyond low temperature expansions. Via a numerical tour de force we have explicitly calculated for the first time the DCF of a solid: based on the fundamental measure concept we provide results for the DCF of a hard sphere crystal. We demonstrate that this function differs at coexistence significantly from its liquid counterpart - both in shape as well as in its order of magnitude - because it is dominated by vacancies. We provide evidence that the traditional use of liquid DCFs in functional Taylor expansions of the free energy is conceptually wrong and show that the emergent elastic constants are in good agreement with simulation-based results.

Using non-equilibrium molecular dynamics simulations we study the yielding behaviour of a model cluster crystal formed by ultrasoft particles under shear. We investigate the evolution of stress as a function of strain for different shear rates, $\dot{\gamma}$, and temperatures. The stress-strain relation displays a pronounced maximum at the yielding point; the height of this maximum, $\sigma_\text{p}$, increases via a power law with an increasing shear range and tends to saturate to a finite value if the limit shear rate goes to zero (at least within the considered temperature range). Interestingly, this behaviour can be captured by the Herschel-Bulkley type model which, for a given temperature, allows us to predict a static yield stress $\sigma^{0}_\text{p}$ (in the shear rate tending to zero limit), a characteristic timescale $\tau_\text{c}$, and the exponent $\alpha$ of the above-mentioned power-law decay of the $\sigma_\text{p}$ at high shear rates. Furthermore, for different temperatures, the $\sigma_\text{p}$ can be scaled as functions of $\dot{\gamma}$ onto a single master curve when scaled by corresponding $\tau_\text{c}$ and ${\sigma}_\text{p}^{0}$. Moreover, for a given shear rate, $\sigma_\text{p}$ displays a logarithmic dependence on temperature. Again, the $\sigma_\text{p}{-}T$ curves for different shear rates can be scaled on a single logarithmic master curve when scaled by a corresponding fitting parameters., Comment: 9 pages, 4 figures, 1 table

Self-assembly into target structures is an efficient material design strategy. Combining analytical calculations and computational techniques of evolutionary and Monte Carlo types, we report about a remarkable structural variability of Wigner bilayer ground states, when charges are confined between parallel charged plates. Changing the inter-layer separation, or the plate charge asymmetry, a cascade of ordered patterns emerges. At variance with the symmetric case phenomenology, the competition between commensurability features and charge neutralization leads to long range attraction, appearance of macroscopic charges, exotic phases, and non conventional phase transitions with distinct critical indices, offering the possibility of a subtle, but precise and convenient control over patterns.

We study the ordered equilibrium structures of patchy particles where the patches are located on the surface of the colloid such that they form a regular tetrahedron. Using optimization techniques based on ideas of evolutionary algorithms we identify possible candidate structures. We retain not only the energetically most favourable lattices but also include a few energetically less favourable particle arrangements (i.e., local minima on the enthalpy landscape). Using suitably developed Monte Carlo based simulations techniques in an NPT ensemble we evaluate the thermodynamic properties of these candidate structures along selected isobars and isotherms and identify thereby the respective ranges of stability. We demonstrate on a quantitative level that the equilibrium structures at a given state point result from a delicate compromise between entropy, energy (i.e., the lattice sum) and packing., Comment: 17 pages, 6 figures J. Phys. Condens. Matter, 24 (2012), in press

We have investigated the effect of a disordered porous matrix on the cluster microphase formation of a two dimensional system where particles interact via competing interactions. To this end we have performed extensive Monte Carlo simulations and have systematically varied the densities of the fluid and of the matrix as well as the interaction between the matrix particles and between the matrix and fluid particles. Our results provide evidence that the matrix does have a distinct effect on the microphase formation of the fluid particles: as long as the particles interact both among themselves as well as with the fluid particles via a simple hard sphere potential, they essentially reduce the available space, in which the fluid particles form a cluster microphase. On the other hand, if we turn on a long-range tail in the matrix-matrix and in the matrix-fluid interactions, the matrix particles become nucleation centers for the clusters formed by the fluid particles., Comment: 12 pages, 6 figures

The rapid progress in precisely designing the surface decoration of patchy colloidal particles offers a new, yet unexperienced freedom to create building entities for larger, more complex structures in soft matter systems. However, it is extremely difficult to predict the large variety of ordered equilibrium structures that these particles are able to undergo under the variation of external parameters, such as temperature or pressure. Here we show that, by a novel combination of two theoretical tools, it is indeed possible to predict the self-assembly scenario of patchy colloidal particles: on one hand, a reliable and efficient optimization tool based on ideas of evolutionary algorithms helps to identify the ordered equilibrium structures to be expected at T = 0; on the other hand, suitable simulation techniques allow to estimate via free energy calculations the phase diagram at finite temperature. With these powerful approaches we are able to identify the broad variety of emerging self-assembly scenarios for spherical colloids decorated by four patches and we investigate and discuss the stability of the crystal structures on modifying in a controlled way the tetrahedral arrangement of the patches., Comment: 11 pages, 7 figures, Soft Matter Communication (accepted)

We analyze the phonon spectra of periodic structures formed by two-dimensional mixtures of dipolar colloidal particles. These mixtures display an enormous variety of complex ordered configurations [J. Fornleitner {\it et al.}, Soft Matter {\bf 4}, 480 (2008)], allowing for the systematic investigation of the ensuing phonon spectra and the control of phononic gaps. We show how the shape of the phonon bands and the number and width of the phonon gaps can be controlled by changing the susceptibility ratio, the concentration and the mass ratio between the two components., Comment: 4 pages 3 figures

We have investigated the phase diagram of the Girifalco model of C60 fullerene in the framework provided by the MHNC and the SCOZA liquid state theories, and by a Perturbation Theory (PT), for the free energy of the solid phase. We present an extended assessment of such theories as set against a recent Monte Carlo study of the same model [D. Costa et al, J. Chem. Phys. 118:304 (2003)]. We have compared the theoretical predictions with the corresponding simulation results for several thermodynamic properties. Then we have determined the phase diagram of the model, by using either the SCOZA, or the MHNC, or the PT predictions for one of the coexisting phases, and the simulation data for the other phase, in order to separately ascertain the accuracy of each theory. It turns out that the overall appearance of the phase portrait is reproduced fairly well by all theories, with remarkable accuracy as for the melting line and the solid-vapor equilibrium. The MHNC and SCOZA results for the liquid-vapor coexistence, as well as for the corresponding critical points, are quite accurate. All results are discussed in terms of the basic assumptions underlying each theory. We have selected the MHNC for the fluid and the first-order PT for the solid phase, as the most accurate tools to investigate the phase behavior of the model in terms of purely theoretical approaches. The overall results appear as a robust benchmark for further theoretical investigations on higher order C(n>60) fullerenes, as well as on other fullerene-related materials, whose description can be based on a modelization similar to that adopted in this work., Comment: RevTeX4, 15 pages, 7 figures; submitted to Phys. Rev. E

Freezing of simple liquid metals and the relative stabilities of competing crystalline solids are investigated using thermodynamic perturbation theory, the interactions between ions being modeled by effective pair potentials derived from pseudopotential theory. The ionic free energy of the solid phase is calculated, to first order in the perturbation potential, using classical density-functional theory and an accurate approximation to the hard-sphere radial distribution function. Free energy calculations for Na, Mg, and Al yield well-defined freezing transitions and structural free energy differences for bcc, fcc, and hcp crystals in qualitative agreement with experiment., Comment: 8 pages, 4 figures, LaTeX with elsart.sty