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

Liquid-gas phase behaviour of an argon-like fluid modelled by the hard-core two-Yukawa potential

We study a model for an argon-like fluid parameterised in terms of a hard-core repulsion and a two-Yukawa potential. The liquid-gas phase behaviour of the model is obtained from the thermodynamically self-consistent Ornstein-Zernike approximation (SCOZA) of Hoye and Stell, the solution of which lends itself particularly well to a pair potential of this form. The predictions for the critical point and the coexistence curve are compared to new high resolution simulation data and to other liquid-state theories, including the hierarchical reference theory (HRT) of Parola and Reatto. Both SCOZA and HRT deliver results that are considerably more accurate than standard integral-equation approaches. Among the versions of SCOZA considered, the one yielding the best agreement with simulation successfully predicts the critical point parameters to within 1%.Comment: 10 pages 6 figure

A liquid state theory that remains successful in the critical region

A thermodynamically self-consistent Ornstein-Zernike approximation (SCOZA) is applied to a fluid of spherical particles with a pair potential given by a hard-core repulsion and a Yukawa attractive tail $w(r)=-\exp [-z(r-1)]/r$. This potential allows one to take advantage of the known analytical properties of the solution to the Ornstein-Zernike equation for the case in which the direct correlation function outside the repulsive core is given by a linear combination of two Yukawa tails and the radial distribution function $g(r)$ satisfies the exact core condition $g(r)=0$ for $r<1$. The predictions for the thermodynamics, the critical point, and the coexistence curve are compared here to other theories and to simulation results. In order to unambiguously assess the ability of the SCOZA to locate the critical point and the phase boundary of the system, a new set of simulations has also been performed. The method adopted combines Monte Carlo and finite-size scaling techniques and is especially adapted to deal with critical fluctuations and phase separation. It is found that the version of the SCOZA considered here provides very good overall thermodynamics and a remarkably accurate critical point and coexistence curve. For the interaction range considered here, given by $z=1.8$, the critical density and temperature predicted by the theory agree with the simulation results to about 0.6%.Comment: Prepared for the John Barker festschrift issue of Molecular Physics. 22 pages Latex, 6 ps figure

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

Self-consistent Ornstein-Zernike approximation for three-dimensional spins

An Ornstein-Zernike approximation for the two-body correlation function embodying thermodynamic consistency is applied to a system of classical Heisenberg spins on a three-dimensional lattice. The consistency condition determined in a previous work is supplemented by introducing a simplified expression for the mean-square fluctuations of the spin on each lattice site. The thermodynamics and the correlations obtained by this closure are then compared with approximants based on extrapolation of series expansions and with Monte Carlo simulations. The comparison reveals that many properties of the model, including the critical temperature, are very well reproduced by this simple version of the theory, but that it shows substantial quantitative error in the critical region, both above the critical temperature and with respect to its rendering of the spontaneous magnetization curve. A less simple but conceptually more satisfactory version of the SCOZA is then developed, but not solved, in which the effects of transverse correlations on the longitudinal susceptibility is included, yielding a more complete and accurate description of the spin-wave properties of the model.Comment: 32 pages, 12 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

Different characteristics of triptans

Despite the pharmacokinetic differences among triptans and the variety of ways of administration, the clinical differences in everyday use of these drugs do not allow a largely accepted decisional tree. There are a number of comparative trials showing similar results with regard to efficacy, safety, and tolerability of these drugs. This means that the patientrsquos preference is one of the most important decisive factors in choosing one triptan over another. A good migraine therapy requires a balance between patient satisfaction and drug efficacy and safety. All the marked triptans show a good benefit-risk ratio, and comorbidity should be considered when choosing between different triptans

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

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

Smooth cutoff formulation of hierarchical reference theory for a scalar phi4 field theory

The phi4 scalar field theory in three dimensions, prototype for the study of phase transitions, is investigated by means of the hierarchical reference theory (HRT) in its smooth cutoff formulation. The critical behavior is described by scaling laws and critical exponents which compare favorably with the known values of the Ising universality class. The inverse susceptibility vanishes identically inside the coexistence curve, providing a first principle implementation of the Maxwell construction, and shows the expected discontinuity across the phase boundary, at variance with the usual sharp cutoff implementation of HRT. The correct description of first and second order phase transitions within a microscopic, nonperturbative approach is thus achieved in the smooth cutoff HRT.Comment: 8 pages, 4 figure