Phase transitions mean field theory

Keywords quantum rotors, phase transition, mean-field theory, solid hydrogen 1. Introduction... 

Phase transitions are defined thermodynamically. However, to model them, we must turn to theories that describe the ordering in the system. This is often done approximately, using the average order parameter (here we assume one will suffice to describe the transition) within a so-called mean field theory. The choice of appropriate order parameter is discussed in the next section. The order parameter for a system is a function of the thermodynamic state of the system (often temperature alone is varied) and is uniform throughout the system and, at equilibrium, is not time dependent. A mean field theory is the simplest approximate model for the dependence of the order parameter on temperature within a phase, as well as for the change in order parameter and thermodynamic properties at a phase transition. Mean field theories date back to when van der Waals introduced his equation of state for the liquid-gas transition. 

Here we review the properties of the model in the mean field theory [328] of the system with the quantum APR Hamiltonian (41). This consists of considering a single quantum rotator in the mean field of its six nearest neighbors and finding a self-consistent condition for the order parameter. Solving the latter condition, the phase boundary and also the order of the transition can be obtained. The mean-field approximation is similar in spirit to that used in Refs. 340,341 for the case of 3D rotators. 

I. Jensen, H. C. Fogedby. Kinetic phase transitions in a surface-reaction model with diffusion Computer simulations and mean-field theory. Phys Rev A 2 1969-1975, 1990. 

Table 7.3 lists the four rules in this minimally-diluted rule-family, along with their corresponding iterative maps. Notice that since rules R, R2 and R3 do not have a linear term, / (p = 0) = 0 and mean-field-theory predicts a first-order phase transition. By first order we mean that the phase transition is discontinuous there is an abrupt, discontinuous change at a well defined critical probability Pc, at which the system suddenly goes from having poo = 0 as the only stable fixed point to having an asymptotic density Poo 7 0 as the only stable fixed point (see below). 

Table 7.4 compares the mean-field-theory prediction for the order of the phase transition and critical probability pc to numerical results obtained by Biduax, et.al. ([bidaux89a], [bidaux89b]) by simulating dynamics on regular lattices of dimension d = I, d = 2 and d = 4. 

Table 7.4 Oi dor of phase transition and threshold probabilities versus space dimension for rules R, ...Rn, as determined by mean-field theory and numerical calculation ([bidaux89a], [bidaux89b]).

Fig. 12 Morphology diagram of PEP-6-PLA. ODTs determined by rheology A, , 0, x ordered microstrue lures directly observed by SAXS A S C 0 G x L. Solid lines ordered range of xN as determined by rheological measurements dashed lines approximate phase-transition boundaries using experimental data and mean-field theory predictions. From [63]. Copyright 2002 Wiley...

Fig. 27. Phase diagram of an adsorbed film in- the simple cubic lattice from mean-fleld calculations (full curves - flrst-order transitions, broken curves -second-order transitions) and from a Monte Carlo calculation (dash-dotted curve - only the transition of the first layer is shown). Phases shown are the lattice gas (G), the ordered (2x1) phase in the first layer, lattice fluid in the first layer F(l) and in the bulk F(a>). For the sake of clarity, layering transitions in layers higher than the second layer (which nearly coincide with the layering of the second layer and merge at 7 (2), are not shown. The chemical potential at gas-liquid coexistence is denoted as ttg, and 7 / is the mean-field bulk critical temperature. While the layering transition of the second layer ends in a critical point Tj(2), mean-field theory predicts two tricritical points 7 (1), 7 (1) in the first layer. Parameters of this calculation are R = —0.75, e = 2.5p, 112 = Mi/ = d/2, D = 20, and L varied from 6 to 24. (From Wagner and Binder .)...

The transition from a stable steady-state solution observed at large p to the oscillatory regime assumes the existence of the critical value of the parameter pc, which defines the point of the kinetic phase transition as p > pc, the fluctuations of the order parameter are suppressed and the standard chemical kinetics (the mean-field theory) could be safely used. However, if p < pc, these fluctuations are very large and begin to dominate the process. Strictly speaking, the region p pc at p > pc is also fluctuation-controlled one since here the fluctuations of the order parameter are abnormally high. 

Phase transition in gels can be affected by applying uniaxial stress. With increasing stress in the region below 1 x 104 N m 2 at gelation, the effects of uniaxial stress was qualitatively described by the mean field theory. The present results clearly indicate the possibility of a uniaxial stress-induced phase transition of gels. 

Fig. 2.44 Phase diagram for a conformationally-symmetric diblock copolymer, calculated using self-consistent mean field theory. Regions of stability of disordered, lamellar, gyroid, hexagonal, BCC and close-packed spherical (CPS), phases are indicated (Matsen and Schick 1994 ). All phase transitions are first order, except for the critical point which is marked by a dot.

Fig. 6.22 Phase diagram for blends of PE and PEP homopolymers (A/j, - 392 and 409 respectively) with a PE-PEP diblock (iVc = 1925) (Bates et al. 1995). Open and filled circles denote experimental phase transitions between ordered and disordered states measured by SANS and rheology respectively. Phase boundaries obtained from self-consistent field calculations are shown as solid lines. The diamond indicates the Lifshitz point (LP), below which an unbinding transition (UT) separates lamellar and two-phase regions in mean field theory.

Self-consistent field theory has recently been employed by Janert and Schick (1996,1997a) to analyse the swelling of diblock lamellar phases with homopolymer. It was shown that a complete unbinding transition, where added homopolymer swells the lamellae, finally leading to a transition to a disordered phase, is predicted by mean field theory. The swelling does not continue without limit. 

We note that even short-range interactions may, however, allow a mean-field scenario, if the system has a tricritical point, where three phases are in equilibrium. A well-known example is the 3He-4He system, where a line of critical points of the fluid-superfluid transition meets the coexistence curve of the 3He-4He liquid-liquid transition at its critical point [33]. In D = 3, tricriticality implies that mean-field theory is exact [11], independently from the range of interactions. Such a mechanism is quite natural in ternary systems. For one or two components it would require a further line of hidden phase transitions that meets the coexistence curve at or near its critical point. 

A major ingredient for an RG treatment is a simple and transparent characterization of the molecular forces driving phase separation. This situation calls for mean-field theories of the ionic phase transition. The past decade has indeed seen the development of several approximate mean-field theories that seem to provide a reasonable, albeit not quantitative, picture of the properties of the RPM. Thus, the major forces driving phase separation seem now to be identified. Moreover, the development of a proper description of fluctuations by GDH theory has gone some way to establish a suitable starting point for RG analysis. Needless to say, these developments are also of prime importance in the more general context of electrolyte theory. 

It has been the merit of Picken (1989, 1990) having modified the Maier-Saupe mean field theory successfully for application to LCPs. He derived the stability of the nematic mesophase from an anisotropic potential, thereby making use of a coupling constant that determines the strength of the orientation potential. He also incorporated influences of concentration and molecular weight in the Maier-Saupe model. Moreover, he used Ciferri s equation to take into account the temperature dependence of the persistence length. In this way he found a relationship between clearing temperature (i.e. the temperature of transition from the nematic to the isotropic phase) and concentration ... 

A superconductor exhibits perfect conductivity (See Section 7.2) and the Meissner effect (See Section 7.3) below some critical temperature, Tc. The transition from a normal conductor to a superconductor is a second-order, phase-transition which is also well-described by mean-field theory. Note that the mean-field condensation is not a Bose condensation nor does it require and energy gap. The mean-field theory is combined with London-Ginzburg-Landau theory through the concentration of superconducting carriers as follows ... 

Fig. 10. Schematic phase diagram of a semi-infinite block copolymer melt for the special case of a perfectly neutral surface (Hj=0). Variables chosen are the surface interaction enhancement parameter (-a) and the temperature T rescaled by chain length (assuming X l/T the ordinate hence is proportional to %c/%). While according to the Leibler [197] mean-field theory a symmetric diblock copolymer transforms from the disordered phase (DIS) at Tcb oc n in a second-order transition to the lamellar phase (LAM), according to the theory of Fredrickson and Helfand [210] the transition is of first-order and depressed by a relative amount of order N 1/3. In the second-order case, the surface orders before the bulk at a transition temperature T (oc l / ) as soon as a is negative [216], and the enhancement...

Before setting out on the exact mean field theory solution to the one-dimensional colloid problem, I wish to emphasize that the existence of the reversible phase transition in the n-butylammonium vermiculite system provides decisive evidence in favor of our model. The calculations presented in this chapter are deeply rooted in their agreement with the experimental facts on the best-studied system of plate macroions, the n-butylammonium vermiculite system [3], We now proceed to construct the exact mean field theory solution to the problem in terms of adiabatic pah-potentials of both the Helmholtz and Gibbs free energies. It is the one-dimensional nature of the problem that renders the exact solution possible. 

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