A density-functional theory study of microphase formation in binary Gaussian mixtures.

We use density-functional theory to study the formation of inhomogeneous phases in a binary mixture of particles interacting by repulsive, athermal Gaussian potentials with suitably chosen strengths and ranges. Both the potential parameters and the free-energy functional are the same as those adopted in a previous investigation by other authors (Archer A J, Likos C N and Evans R 2004 J. Phys.: Condens. Matter 16 L297), but here a fully numerical minimization of the functional is performed, without any assumption about the functional form of the density profile. We find lamellar, rod and cluster phases. In the lamellar phase, the two species arrange into intercalating stripes; in the rod and cluster phases, the minority species is localized at the site of a periodic lattice, either triangular (for rods) or body-centred cubic (for clusters), while the other species is distributed non-uniformly in the remaining region, so that it forms a percolating network. The order of the transition from the homogeneous to the inhomogeneous phase and the phase diagram of the mixture are also discussed.

Path integral Monte Carlo study of 4He clusters doped with alkali and alkali-earth ions.

Path integral Monte Carlo calculations of (4)He nanodroplets doped with alkali (Na(+), K(+) and Cs(+)) and alkali-earth (Be(+) and Mg(+)) ions are presented. We study the system at T = 1 K and between 14 and 128 (4)He atoms. For all studied systems, we find that the ion is well localized at the center of the droplet with the formation of a "snowball" of well-defined shells of localized (4)He atoms forming solid-like order in at least the first surrounding shell. The number of surrounding helium shells (two or three) and the number of atoms per shell and the degree of localization of the helium atoms are sensitive to the type of ion. The number of (4)He atoms in the first shell varies from 12 for Na(+) to 18 for Mg(+) and depends weakly on the size of the droplet. The study of the density profile and of the angular correlations shows that the local solid-like order is more pronounced for the alkali ions with Na(+) giving a very stable icosahedral order extending up to three shells.

Quantum dislocations: the fate of multiple vacancies in two-dimensional solid 4He.

Defects are believed to play a fundamental role in the supersolid state of (4)He. We have studied solid (4)He in two dimensions (2D) as a function of the number of vacancies n(v), up to 30, inserted in the initial configuration at ρ=0.0765 Å( - 2), close to the melting density, with the exact zero-temperature shadow path integral ground state method. The crystalline order is found to be stable also in the presence of many vacancies and we observe two completely different regimes. For small n(v), up to about 6, vacancies form a bound state and cause a decrease of the crystalline order. At larger n(v), the formation energy of an extra vacancy at fixed density decreases by one order of magnitude to about 0.6 K. It is no longer possible to recognize vacancies in the equilibrated state because they mainly transform into quantum dislocations and crystalline order is found almost independently of how many vacancies have been inserted in the initial configuration. The one-body density matrix in this latter regime shows a non-decaying large distance tail: dislocations, that in 2D are point defects, turn out to be mobile, their number is fluctuating, and they are able to induce exchanges of particles across the system mainly triggered by the dislocation cores. These results indicate that the notion of the incommensurate versus the commensurate state loses meaning for solid (4)He in 2D, because the number of lattice sites becomes ill defined when the system is not commensurate. Crystalline order is found to be stable also in 3D in the presence of up to 100 vacancies.

Exact ground state Monte Carlo method for Bosons without importance sampling.

Generally "exact" quantum Monte Carlo computations for the ground state of many bosons make use of importance sampling. The importance sampling is based either on a guiding function or on an initial variational wave function. Here we investigate the need of importance sampling in the case of path integral ground state (PIGS) Monte Carlo. PIGS is based on a discrete imaginary time evolution of an initial wave function with a nonzero overlap with the ground state, which gives rise to a discrete path which is sampled via a Metropolis-like algorithm. In principle the exact ground state is reached in the limit of an infinite imaginary time evolution, but actual computations are based on finite time evolutions and the question is whether such computations give unbiased exact results. We have studied bulk liquid and solid (4)He with PIGS by considering as initial wave function a constant, i.e., the ground state of an ideal Bose gas. This implies that the evolution toward the ground state is driven only by the imaginary time propagator, i.e., there is no importance sampling. For both phases we obtain results converging to those obtained by considering the best available variational wave function (the shadow wave function) as initial wave function. Moreover we obtain the same results even by considering wave functions with the wrong correlations, for instance, a wave function of a strongly localized Einstein crystal for the liquid phase. This convergence is true not only for diagonal properties such as the energy, the radial distribution function, and the static structure factor, but also for off-diagonal ones, such as the one-body density matrix. This robustness of PIGS can be traced back to the fact that the chosen initial wave function acts only at the beginning of the path without affecting the imaginary time propagator. From this analysis we conclude that zero temperature PIGS calculations can be as unbiased as those of finite temperature path integral Monte Carlo. On the other hand, a judicious choice of the initial wave function greatly improves the rate of convergence to the exact results.

Nonuniversal routes to universality: critical phenomena in colloidal dispersions.

We investigate critical phenomena in colloids by means of the renormalization-group based hierarchical reference theory of fluids. We focus on three experimentally relevant model systems: namely, the Asakura-Oosawa model of a colloidal dispersion under the influence of polymer-induced attractive depletion forces; fluids with competing short-range attractive and longer-range repulsive interactions; solutions of star polymers whose pair potential presents both an attractive well and an ultrasoft repulsion at shorter distance. Our results show that the ability to tune the effective interactions between colloidal particles allows one to generate a variety of crossovers to the asymptotic critical behavior, which are not observed in atomic fluids.

Model colloidal fluid with competing interactions: bulk and interfacial properties.

Using a simple mean field density functional theory (DFT), the authors investigate the structure and phase behavior of a model colloidal fluid composed of particles interacting via a pair potential which has a hard core of diameter sigma, is attractive Yukawa at intermediate separations, and is repulsive Yukawa at large separations. The authors analyze the form of the asymptotic decay of the bulk fluid correlation functions, comparing results from DFT with those from the self-consistent Ornstein-Zernike approximation (SCOZA). In both theories the authors find rich crossover behavior, whereby the ultimate decay of correlation functions changes from monotonic to long wavelength damped oscillatory decay on crossing certain lines in the phase diagram or sometimes from oscillatory to oscillatory with a longer wavelength. For some choices of potential parameters the authors find, within the DFT, a lambda line at which the fluid becomes unstable with respect to periodic density fluctuations. SCOZA fails to yield solutions for state points near such a lambda line. The propensity towards clustering of particles, which is reflected by the presence of a long wavelength (>>sigma) slowly decaying oscillatory pair correlation function, and a structure factor that exhibits a very sharp maximum at small but nonzero wave numbers, is enhanced in states near the lambda line. The authors present density profiles for the planar liquid-gas interface and for fluids adsorbed at a planar hard wall. The presence of a nearby lambda transition gives rise to pronounced long wavelength oscillations in the one-body density profiles at both types of interface.

Dynamical arrest and replica symmetry breaking in attractive colloids.

Within the replica symmetry breaking framework developed by Mézard and Parisi we investigate the occurrence of structural glass transitions in a model of fluid characterized by hard sphere repulsion together with short-range attraction. This model is appropriate for the description of a class of colloidal suspensions. The transition line in the density-temperature plane displays a reentrant behavior, in agreement with mode coupling theory and recent molecular dynamics simulations. Quantitative differences are found, together with the absence of the predicted glass-glass transition at high density. We also perform a systematic study of the pure hard-sphere fluid in order to ascertain the accuracy of the adopted method and the convergence of the numerical procedure.

Critical behavior in colloid-polymer mixtures: theory and simulation.

We extensively investigated the critical behavior of mixtures of colloids and polymers via the two-component Asakura-Oosawa model and its reduction to a one-component colloidal fluid using accurate theoretical and simulation techniques. In particular the theoretical approach, hierarchical reference theory [A. Parola and L. Reatto, Adv. Phys. 44, 211 (1995)], incorporates realistically the effects of long-range fluctuations on phase separation giving exponents which differ strongly from their mean-field values, and are in good agreement with those of the three-dimensional Ising model. Computer simulations combined with finite-size scaling analysis confirm the Ising universality and the accuracy of the theory, although some discrepancy in the location of the critical point between one-component and full-mixture description remains. To assess the limit of the pair-interaction description, we compare one-component and two-component results.

Microphase separation in two-dimensional systems with competing interactions.

The formation of clusters in condition of thermodynamic equilibrium can be easily observed both in two and three dimensions. In two dimensions relevant cases include pattern formation in Langmuir monolayers and ferrofluids, while in three dimensions cluster phases have been observed in colloids and in protein solutions. We have analyzed the problem within the scenario of competing interactions: typically, a short-range attractive interaction against a long-range repulsive one. This simplified approach is suggested by the fact that the forces, governing self-organization, act on a length scale which is larger than the molecular size; as a consequence many specific details of the molecules of interest are not necessary for studying the general features of microphases. We have tackled the microphase formation by simulations in bidimensional fluids, exploiting the parallel tempering scheme. In particular, we have analyzed the density range in which the particles arrange in circular domains (droplets), and the temperature range in which the system goes from microphases to the homogeneous fluid phase. As the density increases, the droplet size increases as well, but above a certain density the morphology changes and stripes are formed. Moreover at low density, we observe the formation of a liquidlike phase of disordered droplets; at higher densities, instead, the droplets tend to arrange onto a triangular superlattice. Such a change affects the features of the static structure factor, which gives well defined signatures of the microphase morphology. In each case, the specific heat exhibits a peak close to the transition from microphases to the homogeneous fluid phase, which is due to the breaking up of the clusters. The saturation of the height of the specific heat peak, with the increasing of the system size, suggests the possibility of a Kosterlitz-Thouless transition.

Bose-Einstein condensation of incommensurate solid 4He.

It is pointed out that the simulation computation of energy performed so far cannot be used to decide if the ground state of solid 4He has the number of lattice sites equal to the number of atoms (commensurate state) or if it is different (incommensurate state). The best variational wave function, a shadow wave function, gives an incommensurate state, but the equilibrium concentration of vacancies remains to be determined. We have computed the one-body density matrix in solid 4He for the incommensurate state by means of an exact ground state projector method in which incommensurability occurs spontaneously. We find a vacancy induced Bose-Einstein condensation of about 0.23 atoms per vacancy at a pressure of 54 bar. This means that bulk solid 4He is supersolid at low enough temperature if the exact ground state is incommensurate.

Microscopic approach to critical phenomena at interfaces: an application to complete wetting in the Ising model.

We study how the formalism of the hierarchical reference theory (HRT) can be extended to inhomogeneous systems. HRT is a liquid-state theory which implements the basic ideas of the Wilson momentum-shell renormalization group (RG) to microscopic Hamiltonians. In the case of homogeneous systems, HRT provides accurate results even in the critical region, where it reproduces scaling and nonclassical critical exponents. We applied the HRT to study wetting critical phenomena in a planar geometry. Our formalism avoids the explicit definition of effective surface Hamiltonians but leads, close to the wetting transition, to the same renormalization group equation already studied by RG techiques. However, HRT also provides information on the nonuniversal quantities because it does not require any preliminary coarse graining procedure. A simple approximation to the infinite HRT set of equations is discussed. The HRT evolution equation for the surface free energy is numerically integrated in a semi-infinite three-dimensional Ising model and the complete wetting phase transition is analyzed. A renormalization of the adsorption critical amplitude and of the wetting parameter is observed. Our results are compared to available Monte Carlo simulations.

Star polymers: a study of the structural arrest in the presence of attractive interactions.

Simulations and mode-coupling theory calculations, for a large range of the arm number f and packing fraction eta have shown that the structural arrest and the dynamics of star polymers in a good solvent are extremely rich: the systems show a reentrant melting of the disordered glass nested between two stable fluid phases that strongly resemble the equilibrium phase diagram. Starting from a simple model potential we investigate the effect of the interplay between attractive interactions of different range and ultrasoft core repulsion, on the dynamics and on the occurrence of the ideal glass transition line. In the two cases considered so far, we observed some significant differences with respect to the purely repulsive pair interaction. We also discuss the interplay between equilibrium and nonequilibrium phase behavior. The accuracy of the theoretical tools we utilized in our investigation has been checked by comparing the results with molecular dynamics simulations.

Modulational instability and complex dynamics of confined matter-wave solitons.

We study the formation of bright solitons in a Bose-Einstein condensate of 7Li atoms induced by a sudden change in the sign of the scattering length from positive to negative, as reported in a recent experiment [Nature (London) 417, 150 (2002)]]. The numerical simulations are performed by using the Gross-Pitaevskii equation with a dissipative three-body term. We show that a number of bright solitons is produced and this can be interpreted in terms of the modulational instability of the time-dependent macroscopic wave function of the Bose condensate. In particular, we derive a simple formula for the number of solitons that is in good agreement with the numerical results. We find that during the motion of the soliton train in an axial harmonic potential the number of solitonic peaks changes in time and the density of individual peaks shows an intermittent behavior.

Structural arrest in dense star-polymer solutions.

The dynamics of star polymers is investigated via extensive molecular and Brownian dynamics simulations for a large range of functionality f and packing fraction eta. The calculated isodiffusivity curves display both minima and maxima as a function of eta and minima as a function of f. Simulation results are compared with theoretical predictions based on different approximations for the structure factor. In particular, the ideal glass transition line predicted by mode-coupling theory is shown to exactly track the isodiffusivity curves, offering a theoretical understanding for the observation of disordered arrested states in star-polymer solutions.

Vacancy excitation spectrum in solid 4He and longitudinal phonons.

The first microscopic ab initio calculation of the excitation spectrum of a vacancy in solid 4He is reported. The energy-wave vector dispersion relation has been obtained at melting density within a development of the shadow wave function variational technique. The calculation of the excitation spectrum of a vacancy gives a bandwidth which ranges from 6 to 10 K in the hcp solid 4He, depending on the particular direction of the wave vector of the excitation. The effective mass of the vacancy turns out to be about 0.35 4He masses. We have also computed the spectrum of longitudinal phonons and we find rather good agreement with recent experimental results.

Phase diagram of symmetric binary mixtures at equimolar and nonequimolar concentrations: a systematic investigation.

We consider symmetric binary mixtures consisting of spherical particles with equal diameters interacting via a hard-core plus attractive tail potential with strengths epsilon(ij), i,j=1,2, such that epsilon(11)=epsilon(22)>epsilon(12). The phase diagram of the system at all densities and concentrations is investigated as a function of the unlike-to-like interaction ratio delta=epsilon(12)/epsilon(11) by means of the hierarchical reference theory. The results are related to those of previous investigations performed at equimolar concentration, as well as to the topology of the mean-field critical lines. As delta is increased in the interval 0

Hierarchical reference theory study of the lattice restricted primitive model.

A three dimensional model of point charges, named lattice restricted primitive model (LRPM), is investigated by using the hierachical reference theory of fluids. This approach, which generalizes the momentum renormalization group technique, is shown to capture the physics of the model and provides a quantitative description of the phase diagram. The comparison with recent numerical simulations and with other theoretical approaches is discussed both for the LRPM and for the Blume-Capel model, which can be seen as a screened version of LRPM. The nonuniversal crossover region close to the tricritical point is also discussed.

Construction of an effective Hamiltonian for a three-dimensional Ising universality class.

The asymptotic and preasymptotic critical behavior in fluids, mixtures, and uniaxial magnets is believed to be described by an effective straight phi(4) scalar field theory with suitable, nonuniversal, coupling constants. The critical parameters as well as the extent of crossovers and corrections to the leading critical behavior in physical systems, crucially depends on the choice of these couplings. Here we propose a new method for deriving the effective scalar field theory appropriate to a microscopic model in this universality class. Use is made of the hierarchical reference theory, which implements the basic ideas of Wilson momentum space renormalization group to microscopic Hamiltonians. The effective low-energy field theory is then analyzed by the minimal subtraction scheme of Schloms and Dohm. We discuss the application of this method to the three-dimensional Ising model and to the liquid-vapor phase transition. We make comparison with high-temperature expansion results and with experimental data for rare gas.

Many-body interaction effects on the low-k structure of liquid Kr.

Neutron diffraction measurements and theoretical calculations of the structure factor S(k) of liquid Kr are extended to small k values (k<4 nm(-1)). The results show that many-body interaction contributions have an increasing effect on S(k) as k-->0, reaching at least 40% of the measured intensity. Both the phase diagram and the low-k structural data of dense Kr turn out to be closely reproduced by the hierarchical reference theory if additional many-body forces are taken into account by an augmented strength of the Axilrod-Teller triple-dipole potential. The experimental density derivative of S(k) is also used for a very sensitive test of the theories and interaction models considered here.