Continuous phase transitions

This is demonstrated in Fig. 8.14 for a monolayer of dimyristoylphos-phatidylethanolamine (DMPE). The DMPE layer is floating on a water surface in a Langmuir-Blodgett trough. As the layer is compressed by a floating teflon barrier, solid domains appear (bright areas). This phase transition continues until no dark areas are any longer visible. Since a helium-neon laser has been... 

Phase transitions at which the entropy and enthalpy are discontinuous are called first-order transitions because it is the first derivatives of the free energy that are disconthuious. (The molar volume V= (d(i/d p) j is also discontinuous.) Phase transitions at which these derivatives are continuous but second derivatives of G... 

Flere we discuss the exploration of phase diagrams, and the location of phase transitions. See also [128. 129. 130. 131] and [22, chapters 8-14]. Very roughly we classify phase transitions into two types first-order and continuous. The fact that we are dealing with a finite-sized system must be borne in mind, in either case. 

For both first-order and continuous phase transitions, finite size shifts the transition and rounds it in some way. The shift for first-order transitions arises, crudely, because the chemical potential, like most other properties, has a finite-size correction p(A)-p(oo) C (l/A). An approximate expression for this was derived by Siepmann et al [134]. Therefore, the line of intersection of two chemical potential surfaces Pj(T,P) and pjj T,P) will shift, in general, by an amount 0 IN). The rounding is expected because the partition fiinction only has singularities (and hence produces discontinuous or divergent properties) in tlie limit i—>oo otherwise, it is analytic, so for finite Vthe discontinuities must be smoothed out in some way. The shift for continuous transitions arises because the transition happens when L for the finite system, but when i oo m the infinite system. The rounding happens for the same reason as it does for first-order phase transitions whatever the nature of the divergence in thennodynamic properties (described, typically, by critical exponents) it will be limited by the finite size of the system. 

The nematic to smectic A phase transition has attracted a great deal of theoretical and experimental interest because it is tire simplest example of a phase transition characterized by tire development of translational order [88]. Experiments indicate tliat tire transition can be first order or, more usually, continuous, depending on tire range of stability of tire nematic phase. In addition, tire critical behaviour tliat results from a continuous transition is fascinating and allows a test of predictions of tire renonnalization group tlieory in an accessible experimental system. In fact, this transition is analogous to tire transition from a nonnal conductor to a superconductor [89], but is more readily studied in tire liquid crystal system. 

Micellization is a second-order or continuous type phase transition. Therefore, one observes continuous changes over the course of micelle fonnation. Many experimental teclmiques are particularly well suited for examining properties of micelles and micellar solutions. Important micellar properties include micelle size and aggregation number, self-diffusion coefficient, molecular packing of surfactant in the micelle, extent of surfactant ionization and counterion binding affinity, micelle collision rates, and many others. 

If the gas-flow rate is increased, one eventuaHy observes a phase transition for the abovementioned regimes. Coalescence of the gas bubbles becomes important and a regime with both continuous gas and Hquid phases is reestabHshed, this time as a gas-flUed core surrounded by a predominantly Hquid annular film. Under these conditions there is usuaHy some gas dispersed as bubbles in the Hquid and some Hquid dispersed as droplets in the gas. The flow is then annular. Various qualifying adjectives maybe added to further characterize this regime. Thus there are semiannular, pulsing annular, and annular mist regimes. Over a wide variety of flow rates, the annular Hquid film covers the entire pipe waH. For very low Hquid-flow rates, however, there may be insufficient Hquid to wet the entire surface, giving rise to rivulet flow. 

A fingerprint of a continuous phase transition is the divergence of the correlation length at the critical temperature 7", with for... 

FIG. 14 Phase diagram of the quantum APR model in the Q -T plane. The solid curve shows the line of continuous phase transitions from an ordered phase at low temperatures and small rotational constants to a disordered phase according to the mean-field approximation. The symbols show the transitions found by the finite-size scaling analysis of the path integral Monte Carlo data. The dashed line connecting these data is for visual help only. (Reprinted with permission from Ref. 328, Fig. 2. 1997, American Physical Society.)... 

From (62) and (70) it follows that the Lifshitz and tricritical points coincide giving the Lifshitz tricritical point [18,66] for 7 = 27/4. 7 = 27/4 can be considered, as a borderline value between the weak (7 <27/4) and the strong (7 >27/4) surfactants. For the weak surfactants the tricritical point is located at the transition between the microemulsion and the coexisting uniform oil- and water-rich phases, whereas for the strong surfactants the tcp is located at the transition between the microemulsion and the liquid-crystal phases. The transition between the microemulsion and the ordered periodic phases is continuous for p < Ps < Ps and first order for p > p[. 

Since M is continuous for all values of H and T, this one-dimensional system does not exhibit a phase transition for any positive temperature. ... 

Rule i 4, on the other hand, has both a linear and quadratic term, so that / (p = 0) > 0 in general, and is therefore predicted to have a second order (or continuous) phase transition. Although the mean-field predictions are, of course, dimension-independent, they are expected to become exact as the dimension d —7 oo. In practice, it is often found that there exists a critical dimension dc above which the mean-field critical exponents are recovered exactly. 

As it is pos.sible to continuously transform liquids into ga.ses and vice versa without passing through a phase transition, Langton lumps liquid and gi s phases into tlie more general fluid phase. 

The rapid rise in computer speed over recent years has led to atom-based simulations of liquid crystals becoming an important new area of research. Molecular mechanics and Monte Carlo studies of isolated liquid crystal molecules are now routine. However, care must be taken to model properly the influence of a nematic mean field if information about molecular structure in a mesophase is required. The current state-of-the-art consists of studies of (in the order of) 100 molecules in the bulk, in contact with a surface, or in a bilayer in contact with a solvent. Current simulation times can extend to around 10 ns and are sufficient to observe the growth of mesophases from an isotropic liquid. The results from a number of studies look very promising, and a wealth of structural and dynamic data now exists for bulk phases, monolayers and bilayers. Continued development of force fields for liquid crystals will be particularly important in the next few years, and particular emphasis must be placed on the development of all-atom force fields that are able to reproduce liquid phase densities for small molecules. Without these it will be difficult to obtain accurate phase transition temperatures. It will also be necessary to extend atomistic models to several thousand molecules to remove major system size effects which are present in all current work. This will be greatly facilitated by modern parallel simulation methods that allow molecular dynamics simulations to be carried out in parallel on multi-processor systems [115]. 

As computer power continues to increase over the next few years, there can be real hope that atomistic simulations will have major uses in the prediction of phases, phase transition temperatures, and key material properties such as diffusion coefficients, elastic constants, viscosities and the details of surface adsorption. 

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