Structure and dielectric properties of polar fluids with extended dipoles: results from numerical simulations

The strengths and shortcomings of the point dipole model for polar fluids of spherical molecules are illustrated by considering the physically more relevant case of extended dipoles formed by two opposite charges ±?q separated by a distance d (dipole moment μ=qd). Extensive molecular dynamics simulations on a high-density dipolar fluid are used to analyse the dependence of the pair structure, dielectric constant ε and dynamics as a function of the ratio d/σ (σ is the molecular diameter), for a fixed dipole moment μ. The point dipole model is found to agree well with the extended dipole model up to d/σ ? 0.3. Beyond that ratio, ε shows a non-trivial variation with d/σ. When d/σ > 0.6, a transition is observed towards a hexagonal columnar phase; the corresponding value of the dipole moment is found to be substantially lower than the value of the point dipole required to drive a similar transition.     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998     

On the difference between a point multipole and an equivalent linear arrangement of point charges in force field models for vapour–liquid equilibria; partial charge based models for 59 real fluids

The replacement of a point dipole and a point quadrupole by a corresponding linear arrangement of two point charges (+q, ?q) and accordingly three point charges (+q, ?2q, +q) is studied with respect to vapour–liquid equilibria. The dependence of saturated liquid density, vapour pressure and heat of vaporization on the choice of the distance d between the charges in the point charge arrangement is analysed. For the studied dipolar two-centre Lennard-Jones (2CLJD) and quadrupolar two-centre Lennard-Jones (2CLJQ) models, d/σ between 1/15 and 1/20 is a reasonable compromise between numerical and physical accuracy, where σ is the Lennard-Jones size parameter. The results are used to derive validated partial charge based models of 59 real fluids from previously published point dipole and point quadrupole based models.     

Effect of shape anisotropy on the phase diagram of the Gay-Berne fluid

We have used the density functional theory to study the effect of molecular elongation on the isotropic-nematic, isotropic-smectic A and nematic-smectic A phase transitions of a fluid of molecules interacting via the Gay-Berne intermolecular potential. We have considered a range of length-to-width parameter 3.0 ⩽ x₀ ⩽ 4.0 in steps of 0.2 at different densities and temperatures. Pair correlation functions needed as input information in density functional theory are calculated using the Percus-Yevick integral equation theory. Within the small range of elongation, the phase diagram shows significant changes. The fluid at low temperature is found to freeze directly from isotropic to smectic A phase for all the values of x₀ considered by us on increasing the density while the nematic phase stabilizes in between isotropic and smectic A phases only at high temperatures and densities. Both isotropic-nematic and nematic-smectic A transition density and pressure are found to decrease as we increase x₀. The phase diagram obtained is compared with computer simulation result of the same model potential and is found to be in good qualitative agreement.     

Dimensionality Effects on the Mixed Spin-1/2 and Spin-2 Blume-Capel Model: Renormalization Group Theory

We have used the real-space Migdal-Kadanoff renormalization group technique on d-dimensional hypercubic lattice to study the mixed spin-1/2 and spin-2 Blume-Capel model. First, we indicate a critical dimension d_C ≈?2.05, above and below which different topologies of phase diagrams occur. The phase diagrams have been plotted in the (crystal field, temperature) plane around d_C, in which there is a second-order phase transition. Moreover, using the variation of the free energy at low temperatures, we have established the ground-state phase diagrams in the (?/J, C/J) plane for d?<?d_C and d?≥?d_C. In particular, we have seen the appearance of two first-order transitions at very low temperatures by the use of the free energy and its isotherm derivative. A detailed analysis of fixed points and flow diagrams indicates that there is no tricritical point.

     

Study of the solid-liquid-vapour phase equilibria of flexible chain molecules using Wertheim's thermodynamic perturbation theory

The phase diagram of flexible molecules formed by freely-jointed tangent spheres is studied using the first-order thermodynamic perturbation theory of Wertheim for both fluid and solid phases. A mean-field term is added to the free energy of the fluid and solid phase in order to account for attractive dispersion forces. The approach is used to determine the global (solid-liquid-vapour) phase diagrams and triple points of chain molecules of increasing chain length. It is found that the triple point temperature is not affected strongly by the length of the chain, whereas the gas-liquid critical temperature increases dramatically. The asymptotic limits of the phase diagram for infinitely long chains are discussed. The reduced critical temperature of infinitely long chains as given by the mean-field theory is 2/3, and the reduced triple point temperature is 0.048 56, so that an asymptotic value of T _t/T _c = 0.07284 for the ratio of the triple to critical point temperatures is obtained. This indicates that fully-flexible tangent chains present an enormous liquid range. The proposed theory, while being extremely simple, provides a useful insight into the phase behaviour of chain molecules, showing the existence of finite asymptotic limits for the triple and critical point temperatures. However, since n-alkanes present an asymptotic limit of about T _t/T _c, = 0.40, the agreement With experiment is not quantitative. This suggests that fully flexible models may not be appropriate to model the solid phases of real chain molecules.     

Polymer mixtures in confined geometries: Model systems to explore phase transitions

While binary (A,B) symmetric polymer mixtures ind = 3 dimensions have an unmixing critical point that belongs to the 3d Ising universality class and crosses over to mean field behavior for very long chains, the critical behavior of mixtures confined into thin film geometry falls in the 2d Ising class irrespective of chain length. The critical temperature always scales linearly with chain length, except for strictly two-dimensional chains confined to a plane, for whichT _c ∝N ^5/8 (this unusual exponent describes the fractal contact line between segregated chains in dense melts in two spatial dimensions,d = 2). When the walls of the thin film are not neutral, but preferentially attract one species, complex phase diagrams occur due to the interplay between capillary condensation and wetting phenomena. For ‘competing walls’ (one wall prefers A, the other prefers B) particularly interesting interface localization-delocalization transitions occur, while analogous phenomena in wedges are related to the ‘filling transition’.     

Minimal dipole charge for a dipole-bound dianion

Full configuration interaction calculations for two electrons moving in the field of a fixed finite dipole (FFD) have been carried out, in order not only to determine the conditions for stability relative to one electron detachment, but also to check whether a true dipole-bound system, converse to a Stark-shifted atom-like system, is generated. The FFD model is constructed by placing two point charges of absolute value q, and opposite sign, separated by a distance d.

It has been found that, although dipole charges as small as q≈0.91 au can bind two electrons stronger than one for large enough values of d (thus giving stable systems relative to the detachment of one electron), it is only for q > 2.941 au that the length of the dipole is short enough for the size of the electronic cloud to actually exceed it, so that the system can really be regarded as a dipole-bound dianion, and not a Stark-shifted atom.     

Wake effect in interactions of dipolar molecules with doped graphene

We study the wake effect in the charge carrier density in free graphene induced by an electric dipole moving parallel to it by using the dynamic polarization function of graphene within the random phase approximation for its π electrons described as Dirac?s fermions. We show that, while the equilibrium doping density of graphene sets a length scale for the period of the wake via graphene?s Fermi wavenumber, qualitative properties of the wake are strongly affected by the speed of the dipole, its distance from graphene, and the dipole moment orientation.     

First-principles electronic structure of rare-earth arsenides

The electronic properties of rare-earth arsenides have been calculated from first principles. In the calculations we have treated the rare-earth f electrons both as core-like and as valence-like electrons. We consider the changes in the energy bands and in the density of states near the Fermi level which are found to be relevant, except for the case of LuAs, and discuss this in relation with the role played from the rare-earth 5d derived states. Moreover we show that the rare-earth 5d related bands are particularly sensitive to the variation of the lattice constant; change in the lattice constant of less than 1% leads to a different behaviour with respect to the crossing of the rare-earth 5d derived bands and the As 4p derived bands along the Δ-direction. This point is discussed in connection with the possibility of having a semimetal-semiconductor transition in the rare-earth arsenides. Received 22 February 2001     

Quantum rotors with regular frustration and the quantum Lifshitz point

We have discussed the zero-temperature quantum phase transition in n-component quantum rotor Hamiltonian in the presence of regular frustration in the interaction. The phase diagram consists of ferromagnetic, helical and quantum paramagnetic phase, where the ferro-para and the helical-para phase boundary meets at a multicritical point called a (d,m) quantum Lifshitz point where (d,m) indicates that the m of the d spatial dimensions incorporate frustration. We have studied the Hamiltonian in the vicinity of the quantum Lifshitz point in the spherical limit and also studied the renormalisation group flow behaviour using standard momentum space renormalisation technique (for finite n). In the spherical limit ()one finds that the helical phase does not exist in the presence of any nonvanishing quantum fluctuation for m =d though the quantum Lifshitz point exists for all d > 1+m/2, and the upper critical dimensionality is given by d _u = 3 +m/2. The scaling behaviour in the neighbourhood of a quantum Lifshitz point in d dimensions is consistent with the behaviour near the classical Lifshitz point in (d+z) dimensions. The dynamical exponent of the quantum Hamiltonian z is unity in the case of anisotropic Lifshitz point (d>m) whereas z=2 in the case of isotropic Lifshitz point (d=m). We have evaluated all the exponents using the renormalisation flow equations along-with the scaling relations near the quantum Lifshitz point. We have also obtained the exponents in the spherical limit (). It has also been shown that the exponents in the spherical model are all related to those of the corresponding Gaussian model by Fisher renormalisation. Received: 23 December 1997 / Received in final form: 6 January 1998 / Accepted: 7 January 1998     

Non-equilibrium behavior at a liquid-gas critical point

Second-order phase transitions in a non-equilibrium liquid-gas model with reversible mode couplings, i.e., model H for binary-fluid critical dynamics, are studied using dynamic field theory and the renormalization group. The system is driven out of equilibrium either by considering different values for the noise strengths in the Langevin equations describing the evolution of the dynamic variables (effectively placing these at different temperatures), or more generally by allowing for anisotropic noise strengths, i.e., by constraining the dynamics to be at different temperatures in d _|| - and d _⊥-dimensional subspaces, respectively. In the first, isotropic case, we find one infrared-stable and one unstable renormalization group fixed point. At the stable fixed point, detailed balance is dynamically restored, with the two noise strengths becoming asymptotically equal. The ensuing critical behavior is that of the standard equilibrium model H. At the novel unstable fixed point, the temperature ratio for the dynamic variables is renormalized to infinity, resulting in an effective decoupling between the two modes. We compute the critical exponents at this new fixed point to one-loop order. For model H with spatially anisotropic noise, we observe a critical softening only in the d _⊥-dimensional sector in wave vector space with lower noise temperature. The ensuing effective two-temperature model H does not have any stable fixed point in any physical dimension, at least to one-loop order. We obtain formal expressions for the novel critical exponents in a double expansion about the upper critical dimension d _c = 4 - d _|| and with respect to d _|| , i.e., about the equilibrium theory. Received 4 April 2002 Published online 13 August 2002     

Phase behavior of a suspension of hard spherocylinders plus ideal polymer chains

We study isotropic-isotropic and isotropic-nematic phase transitions of fluid mixtures containing hard spherocylinders (HSC) and added non-adsorbing ideal polymer chains using scaled particle theory (SPT). First, we investigate isotropic-nematic (I -N phase coexistence using SPT in the absence of polymer. We compare the results obtained using a Gaussian form of the orientational distribution function (ODF) to minimize the free energy versus minimizing numerically. We find that formal numerical minimization gives results that are much closer to computer simulation results. In order to describe mixtures of HSC plus ideal chains we studied the depletion of ideal chains around a HSC. We analyze the density profiles of ideal chains near a hard cylinder and find the depletion thickness δ is a function of the ratio of the polymer's radius of gyration R_g and the cylinder radius R_c. Our results are compared with a common approximation in which the depletion thickness is taken equal to the radius of gyration of the polymer chain. We incorporate the correct depletion thickness into SPT and find that for R _g/R _c < 1.56 using ideal chains gives phase transitions at smaller polymer concentrations, whereas for R _g/R _c > 1.56 , which is a common experimental situation, the phase transitions are found at larger polymer concentrations with respect to δ = R _g . The differences are significant, especially for R _g ≫ R _c , so we can conclude it is essential to take into account the properties of ideal polymer chains and the resulting depletion near a cylinder. Finally, we present phase diagrams for rod-polymer mixtures which could be realized under experimental conditions.     

Critical dynamics and multifractal exponents at the Anderson transition in 3d disordered systems

We investigate the dynamics of electrons in the vicinity of the Anderson transition in d = 3 dimensions. Using the exact eigenstates from a numerical diagonalization, a number of quantities related to the critical behavior of the diffusion function are obtained. The relation η = d ? D₂ between the correlation dimension D₂ of the multifractal eigenstates and the exponent η which enters into correlation functions is verified. Numerically, we have η ≈? 1.3. Implications of critical dynamics for experiments are predicted. We investigate the long-time behavior of the motion of a wave packet. Furthermore, electron-electron and electron-phonon scattering rates are calculated. For the latter, we predict a change of the temperature dependence for low T due to η. The electron-electron scattering rate is found to be linear in T and depends on the dimensionless conductance at the critical point.     

Molecular dynamics simulation for the baryon-quark phase transition at finite baryon density

We study the baryon-quark phase transition in the molecular dynamics (MD) of the quark degrees of freedom at finite baryon density. The baryon state at low baryon density, and the deconfined quark state at high baryon density are reproduced. We investigate the equations of state of matters with different u-d-s compositions. It is found that the baryon-quark transition is sensitive to the quark width.     

The incompressible Navier–Stokes equations from black hole membrane dynamics

We consider the dynamics of a d+1 space–time dimensional membrane defined by the event horizon of a black brane in (d+2)-dimensional asymptotically Anti-de Sitter space–time and show that it is described by the d-dimensional incompressible Navier–Stokes equations of non-relativistic fluids. The fluid velocity corresponds to the normal to the horizon while the rate of change in the fluid energy is equal to minus the rate of change in the horizon cross-sectional area. The analysis is performed in the Membrane Paradigm approach to black holes and it holds for a general non-singular null hypersurface, provided a large scale hydrodynamic limit exists. Thus we find, for instance, that the dynamics of the Rindler acceleration horizon is also described by the incompressible Navier–Stokes equations. The result resembles the relation between the Burgers and KPZ equations and we discuss its implications.     

Colour conductivity of hard spheres

We present an analytic solution for the d-dimensional (d > 1) hard-sphere free flight trajectories in a thermostatted colour field. The solution shows that particles can only reach a finite distance in the direction perpendicular to the field in the absence of collisions. Using a numerical algorithm we designed to simulate many-body hard-sphere systems with curved trajectories, we study the onset of the instability leading to phase separation in the two-dimensional case for a range of field strengths and three densities. For the two fluid densities we find that phase separation occurs for sufficiently strong fields regardless of the initial configuration, and that the phase-separated state eventually becomes a collisionless, non-ergodic steady state. For solid densities the phase-separated configuration is stable and conducting, but is not an attractor for other charge distributions because of the impossibility of particle rearrangement.     

Topology and Phase Transitions: The Case of the Short Range Spherical Model

We characterize the topology of the phase space of the Berlin-Kac spherical model in the context of the so called Topological Hypothesis, for spins lying in hypercubic lattices of dimension d. For zero external field we are able to characterize the topology exactly, up to homology. We find that, even though there is a continuum of changes in the topology of the corresponding manifolds, for d ≥ 3 there are abrupt discontinuities in some topological functions that could be good candidates to associate with the phase transitions that occur at the thermodynamic level. We show however that these changes do not coincide with the phase transitions and conversely, that no topological discontinuity can be associated to the points where the phase transitions take place. At variance with what happens in the Mean Field version of this same model, we show that these abrupt topological changes are accessible thermodynamically. We conclude that, even in short range systems, the topological mechanism does not seem to be responsible for the triggering of a phase transition. We also analyze the case of spins connected to a macroscopic number of (but not all) neighbors, and find that, similar to the results found for the fully connected version, in this case the topological hypothesis seems to hold: the phase transition coincides with an accumulation point of the topological changes present in configuration space. The question of the ensemble equivalence in the short range spherical model is also considered.     

The Shear‐Dependent Phase Separation Behavior of the Ternary Blend Polystyrene/Polyvinyl Methyl Ether/Styrene–Acrylonitrile Copolymer

The phase behavior and phase separation dynamics of a PS/PVME/SAN ternary blend using light scattering under a shear rate range of 0.1～40 s^?1 were investigated. The cloud point temperature first increases and then decreases with the increase of shear rates. At higher shear rates, the cloud point temperature again increases. The phase separation behavior in the early and later stages under shear field can be explained by the Cahn–Hilliard theory and the exponential growth law, respectively. The delay time τ _d ?, the apparent diffusion coefficient D _app, the growth rate R(q), and the exponent term show strong dependence on the difference between the experimental temperature and the cloud point temperature (ΔT), and on the shear rates. Compared with PS/PVME binary blends at lower shear rates, τ _d for a PS/PVME/SAN ternary blend is smaller, while at higher shear rates τ _d is larger. At higher shear rates, the introduction of the third component SAN to a PS/PVME binary blends slows the phase separation process.     

Dynamical properties of constrained drops

In this communication we analyze the behavior of excited drops contained in spherical volumes. We study different properties of the dynamical systems, i.e. the maximum Lyapunov exponent MLE, the asymptotic distance in momentum space d _∞ and the normalized variance of the maximum fragment. It is shown that the constrained system behaves as undergoing a first-order phase transition at low densities while as a second-order one at high densities. The transition from liquid-like to vapor-like behavior is signaled both by the caloric curves, the thermal response functions and the MLE. The relationship between the MLE, d _∞, and the caloric curve is explored. Received: 28 March 2002 / Accepted: 17 May 2002