A Primer to the Theory of Critical Phenomena

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Preface

Jurgen M. Honig; Józef Spałek     

This book is intended to be an introduction to the basic theoretical background for the general area of critical phenomena taking place near a continuous phase transition. These phenomena encompass a singular behavior of physical properties, that is, the behavior of measurable physical quantities that may take infinite values at the critical point (e.g., at the critical temperature). Although many books and review articles already deal with this topic, they are often written at an advanced level of mathematical sophistication. We therefore attempted to provide the necessary background information readers will need to study the advanced presentations. Particular emphasis is placed on developing the concept of the order parameter and on a systematic approach starting from Landau mean-field theory.

We generally have tried to keep the discussion at a reasonably elementary level. Some familiarity with the elements of quantum mechanics, Fourier series and transforms, and complex variables is assumed. However, we have not hesitated to include some specialty topics relevant to our aim; this more advanced material, marked with (⁎), can be omitted on a first reading. Also, to render the individual chapters more self-contained, we have repeated some presentations in different chapters. Although we have tried to be careful, nothing can ever be expected to be error-free. We will therefore appreciate being informed where we have been remiss.

format and editing the figures.

This project was partly supported by The National Science Centre (NCN) through Grant MAESTRO, No. DEC-2012/04/A/ST3/00342.

West Lafayette–Kraków, 2016–2017

Chapter 1

Introduction: Classical Phases and Critical Points

Abstract

Phase transitions, and critical phenomena in particular, remain among the most spectacular properties in physics, materials science, and in other disciplines. At the transition materials in this category display mathematical singularities (infinities) in measurable physical quantities such as the specific heat, the bulk compressibility, or the magnetic susceptibility. What is equally important, when the critical point is approached these systems exhibit infinite fluctuations at all scales. At the same time, a surprising universality of these phenomena is observed, which are assembled into so-called universality classes. In this chapter, elementary experimental observations are briefly summarized to exemplify the principal characteristics of discontinuous vs. continuous classical phase transitions, i.e., those driven by thermodynamic fluctuations of the ordering process, as illustrated more precisely in later chapters.

Keywords

Coexistence of phases; Phase diagrams; Range of stability; Triple point; Density fluctuations; Heat of water vaporization; Magnetization of iron and nickel; Fluctuating size of second components near criticality; Universality classes; Collapse of data near the critical point; Scaled thermodynamic and magnetization properties; Lambda transition in liquid helium; Specific heat of normal-superfluid He; Verwey transition

Phase transitions, and critical phenomena in particular, remain among the most spectacular properties in physics, materials science, and in other disciplines. At the transition materials in this category display mathematical singularities (infinities) in measurable physical quantities such as the specific heat, the bulk compressibility, or the magnetic susceptibility. What is equally important, when the critical point is approached these systems exhibit infinite fluctuations at all scales. At the same time, a surprising universality of these phenomena is observed, which are assembled into so-called universality classes. In this chapter, elementary experimental observations are briefly summarized to exemplify the principal characteristics of discontinuous vs. continuous classical phase transitions, i.e., those driven by thermodynamic fluctuations of the ordering process, as illustrated more precisely in later chapters.

1.1 Physical Examples: Macroscopic Properties

We start with a macroscopic characterization of phase transitions. Everyday life is heavily dependent on the presence of water in its three manifestations as vapor, liquid, and solid. Each of these is referred to as a phase, a state of matter with uniform properties at equilibrium, that extend over a large region of space.¹ The phases are defined by their borders at which the measurable physical properties exhibit either singularities or discontinuities. The temperature T and pressure P can be independently varied over a wide range of conditions without affecting the overall appearance of each phase. However, there exist conditions where two of these phases do coexist, under circumstances where T and P can no longer be independently altered. This situation is displayed pictorially via a P–T phase diagram for water, as shown on a log–log scale in Fig. 1.1A and on a semilogarithmic scale in Fig. 1.1B. The curves represent the phase boundaries, i.e., the P–T dependence that must be met for the phase coexistence. Of special relevance to the entire topic of this book is the L-G branch that terminates at the so-called critical point , where the meniscus separating liquid from vapor disappears entirely, indicative of the merging of liquid and vapor into a single entity termed a critical fluid. Just ahead of this event the system changes from a translucent to a cloudy (misty) appearance; this is due to almost uninhibited fluctuations in density that generate condensed clusters of size comparable to or larger than the wavelength of visible light, which scatter incident radiation. For completeness, we mention the triple point ), at which all the three phases coexist.

Figure 1.1 (A) Schematic phase diagram for water, depicting the range of stability of solid (S), liquid (L), and vapor (G). CP denotes the critical point; the triple point (TP) where the three phases coexist is also marked. This sketch serves as a template for phase diagrams for a huge variety of materials present under normal conditions. (B) Same phase diagram for water on a semilogarithmic scale.

Another indicator of the approach of water to critical conditions is the change in its latent heat of vaporization L reflects the discontinuity in all physical properties of water as the liquid is converted to vapor. This process is generally referred to as a first-order (discontinuous) phase transition. Fig. 1.2 displays the progressive decrease of L with rising T . On crossing that temperature, the density of the system changes continuously, but other properties exhibit singularities, a process referred to as a continuous phase transition.² The precise manner of this coalescence is one instance of the more general study of continuous phase transitions in which we shall be interested at length.

Figure 1.2 Latent heat of vaporization L of water as a function of temperature T at the critical pressure P c . The end solid point marks the critical point at which the specific heat is singular, not just discontinuous as characterized by a latent heat L .

A different hallmark of criticality is the existence of large spatial scale fluctuations. This reflects the inherent instability of the system close to criticality, to be documented in later chapters. Under these conditions, water and steam can be interconverted with negligible changes in the enthalpy. The process results in the presence of islands of water of widely variable size coexisting with steam as the critical point is approached. The constant bombardment of the condensed islands by gaseous water molecules gives rise to wild alterations in the local density of the system.

The above discussion obviously applies with appropriate changes to other systems. Fig. 1.1A then becomes a sort of generic phase diagram that displays the P–T for water.

It may come as a surprise that completely different physical systems exhibit analogous if not exactly the same critical phenomena. Prominent among these are ferromagnetic materials. Fig. 1.3 displays the spontaneous magnetization M of metallic iron and nickel as a function of temperature T . Ignoring complications arising from magnetic domain structures, we note with rising T a continuous decrease in Mfor iron and nickel, respectively). Above this temperature, the material is in the paramagnetic, nanopolarized regime. The above reflects the gradual change with T ; with rising T. It turns out that the theoretical analysis for the critical characteristics of both classes of materials is the same. This certainly should pique our interest. Later we introduce the so-called universality classes of critical behavior.

Figure 1.3 Schematic representation of the relative spontaneous magnetization of impure Fe and Ni as functions of temperature. Note the steep decline close to their respective Curie temperatures T c with an infinite slope at that point.

Another feature is worth noting: , as is predicted from the venerable van der Waals equation of state. This discrepancy in β is called the Guggenheim phase diagram, illustrating the so-called principle of corresponding states (Guggenheim,