Fluctuations and Pattern Formation in Fluids with Competing Interactions

One of the most interesting phenomena in the soft-matter realm consists in the spontaneous formation of super-molecular structures (microphases) in condition of thermodynamic equilibrium. A simple mechanism responsible for this self-organization or pattern formation is based on the competition between attractive and repulsive forces with different length scales in the microscopic potential, typically, a short-range attraction against a longer-range repulsion. We analyse this problem by simulations in 2D fluids. We find that, as the temperature is lowered, liquid-vapor phase separation is inhibited by the competition between attraction and repulsion, and replaced by a transition to non-homogeneous phases. The structure of the fluid shows well defined signatures of the presence of both intra- and inter-cluster correlations. Even when the competition between attraction and repulsion is not so strong as to cause microphase formation, it still induces large density fluctuations in a wide region of the temperature-density plane. In this large-fluctuation regime, pattern formation can be triggered by a weak external modulating field.Comment: To appear in the proceedings of the "International workshop on collective phenomena in macroscopic systems", 2006 Villa Olmo (Como), Ital

Phase diagram of symmetric binary mixtures at equimolar and non-equimolar 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 (HRT). 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 < delta < 1, we find first a regime where the phase diagram at equal species concentration displays a tricritical point, then one where both a tricritical and a liquid-vapor critical point are present. We did not find any clear evidence of the critical endpoint topology predicted by mean-field theory as delta approaches 1, at least up to delta=0.8, which is the largest value of delta investigated here. Particular attention was paid to the description of the critical-plus-tricritical point regime in the whole density-concentration plane. In this situation, the phase diagram shows, in a certain temperature interval, a coexistence region that encloses an island of homogeneous, one-phase fluid.Comment: 27 pages + 20 figure

Phase transitions in simple and not so simple binary fluids

Compared to pure fluids, binary mixtures display a very diverse phase behavior, which depends sensitively on the parameters of the microscopic potential. Here we investigate the phase diagrams of simple model mixtures by use of a microscopic implementation of the renormalization group technique. First, we consider a symmetric mixture with attractive interactions, possibly relevant for describing fluids of molecules with internal degrees of freedom. Despite the simplicity of the model, slightly tuning the strength of the interactions between unlike species drastically changes the topology of the phase boundary, forcing or inhibiting demixing, and brings about several interesting features such as double critical points, tricritical points, and coexistence domains enclosing `islands' of homogeneous, mixed fluid. Homogeneous phase separation in mixtures can be driven also by purely repulsive interactions. As an example, we consider a model of soft particles which has been adopted to describe binary polymer solutions. This is shown to display demixing (fluid-fluid) transition at sufficiently high density. The nature and the physical properties of the corresponding phase transition are investigated.Comment: 6 pages + 3 figures, presented at the 5th EPS Liquid Matter Conference, Konstanz, 14-18 September 200

Anisotropy effects on the magnetic excitations of a ferromagnetic monolayer below and above the Curie temperature

The field-driven reorientation transition of an anisotropic ferromagnetic monolayer is studied within the context of a finite-temperature Green's function theory. The equilibrium state and the field dependence of the magnon energy gap $E_0$ are calculated for static magnetic field $H$ applied in plane along an easy or a hard axis. In the latter case, the in-plane reorientation of the magnetization is shown to be continuous at T=0, in agreement with free spin wave theory, and discontinuous at finite temperature $T>0$, in contrast with the prediction of mean field theory. The discontinuity in the orientation angle creates a jump in the magnon energy gap, and it is the reason why, for $T>0$, the energy does not go to zero at the reorientation field. Above the Curie temperature $T_C$, the magnon energy gap $E_0(H)$ vanishes for H=0 both in the easy and in the hard case. As $H$ is increased, the gap is found to increase almost linearly with $H$, but with different slopes depending on the field orientation. In particular, the slope is smaller when $H$ is along the hard axis. Such a magnetic anisotropy of the spin-wave energies is shown to persist well above $T_C$ ($T \approx 1.2 T_C$).Comment: Final version accepted for publication in Physical Review B (with three figures

A model colloidal fluid with competing interactions: bulk and interfacial properties

Using a simple mean-field density functional theory theory (DFT), we investigate the structure and phase behaviour 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 repulsive Yukawa at large separations. We analyse the form of the asymptotic decay of the bulk fluid correlation functions, comparing results from our DFT with those from the self consistent Ornstein-Zernike approximation (SCOZA). In both theories we find rich crossover behaviour, 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 we 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 to clustering of particles, which is reflected by the presence of a long wavelength $\gg \sigma$, slowly decaying oscillatory pair correlation function, and a structure factor that exhibits a very sharp maximum at small but non zero wavenumbers, is enhanced in states near the $\lambda$-line. We 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 densities at both types of interface.Comment: 14 pages, 11 figure

Recent developments of the Hierarchical Reference Theory of Fluids and its relation to the Renormalization Group

The Hierarchical Reference Theory (HRT) of fluids is a general framework for the description of phase transitions in microscopic models of classical and quantum statistical physics. The foundations of HRT are briefly reviewed in a self-consistent formulation which includes both the original sharp cut-off procedure and the smooth cut-off implementation, which has been recently investigated. The critical properties of HRT are summarized, together with the behavior of the theory at first order phase transitions. However, the emphasis of this presentation is on the close relationship between HRT and non perturbative renormalization group methods, as well as on recent generalizations of HRT to microscopic models of interest in soft matter and quantum many body physics.Comment: 17 pages, 5 figures. Review paper to appear in Molecular Physic

Surface magnetic canting in a ferromagnet

The surface magnetic canting (SMC) of a semi-infinite film with ferromagnetic exchange interaction and competing bulk and surface anisotropies is investigated via a nonlinear mapping formulation of mean-field theory previously developed by our group [L. Trallori et al., Int. J. Mod. Phys. B 10, 1935-1988 (1996)], and extended to the case where an external magnetic field is applied to the system. When the field H is parallel to the film plane, the condition for SMC is found to be the same as that recently reported by Popov and Pappas [Phys. Rev. B 64, 184401 (2001)]. The case of a field H applied perpendicularly to the film plane is also investigated. In both cases, the zero-temperature equilibrium configuration is easily determined by our theoretical approach.Comment: 4 pages, 3 figure

Theory for the phase behaviour of a colloidal fluid with competing interactions

We study the phase behaviour of a fluid composed of particles which interact via a pair potential that is repulsive for large inter-particle distances, is attractive at intermediate distances and is strongly repulsive at short distances (the particles have a hard core). As well as exhibiting gas-liquid phase separation, this system also exhibits phase transitions from the uniform fluid phases to modulated inhomogeneous fluid phases. Starting from a microscopic density functional theory, we develop an order parameter theory for the phase transition in order to examine in detail the phase behaviour. The amplitude of the density modulations is the order parameter in our theory. The theory predicts that the phase transition from the uniform to the modulated fluid phase can be either first order or second order (continuous). The phase diagram exhibits two tricritical points, joined to one another by the line of second order transitions.Comment: 12 pages, 9 figures. Accepted for publication in J. Phys. Condens. Matte