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Cambridge University Press eBooks

Phase transitions and critical phenomena

J. P. Casquilho, P. I. C. Teixeira

Published Dec 23, 2014• 1,207 citations
Publisher

Abstract

Introduction In this chapter we provide a comprehensive and unified treatment of the physical concepts and quantities relevant to phase transitions and critical phenomena. Some of these concepts and quantities have already been discussed in the particular contexts of magnetism (Chapter 7), or liquid crystals (Chapter 9, We conclude the chapter with a brief reference to the application of renormalisation group ideas to critical phenomena. The resulting reconciliation of the predictions of classical theories with experiments and exact or quasi-exact solutions of model systems is a major triumph of twentieth-century physics. Phases and phase transitions Thermodynamics habitually deals with equilibrium systems that are uniform on the macroscopic scale – i.e., where the structure, density and composition are the same throughout the bulk of the system, which is many times greater than a single atom or molecule. Because the system is in equilibrium, intensive thermodynamic variables such as the temperature or chemical potential are also spatially uniform. Such a system is said to consist of a single phase – it is a one-phase system. Phases are what used to be called the states of matter. Solids, liquids, gases and plasmas are four commonly occurring phases – they correspond to the four elements of Aristotelian physics: earth, water, air and fire, respectively. There are, however, many other, less easily identified phases, some of which we have already encountered in this book, such as the ferromagnetic, antiferromagnetic, nematic or superconducting phases. On varying the temperature, pressure and chemical potential(s) of a system, properties such as its structure, density, composition, compressibility, specific heat, etc., in general change smoothly. Yet under certain conditions the changes may be abrupt – some of these properties may exhibit discontinuities, or even divergences, at a phase transition . Phase transitions are among the most spectacular phenomena of nature. Consider, for instance, the phase sequence of water on heating: from ice, an opaque, slippery, rock-like solid; to colourless, incompressible, liquid water, which nevertheless easily flows under gravity; to water vapour, an invisible and very low-density (greenhouse!) gas, hence of ill-defined volume.

DOI
10.1017/cbo9781107284180.011

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Introduction In this chapter we provide a comprehensive and unified treatment of the physical concepts and quantities relevant to phase transitions and critical phenomena. Some of these concepts and quantities have already been discussed in the particular contexts of magnetism (Chapter 7), or liquid crystals (Chapter 9, We conclude the chapter with a brief reference to the application of renormalisation group ideas to critical phenomena. The resulting reconciliation of the predictions of classical theories with experiments and exact or quasi-exact solutions of model systems is a major triumph of twentieth-century physics. Phases and phase transitions Thermodynamics habitually deals with equilibrium systems that are uniform on the macroscopic scale – i.e., where the structure, density and composition are the same throughout the bulk of the system, which is many times greater than a single atom or molecule. Because the system is in equilibrium, intensive thermodynamic variables such as the temperature or chemical potential are also spatially uniform. Such a system is said to consist of a single phase – it is a one-phase system. Phases are what used to be called the states of matter. Solids, liquids, gases and plasmas are four commonly occurring phases – they correspond to the four elements of Aristotelian physics: earth, water, air and fire, respectively. There are, however, many other, less easily identified phases, some of which we have already encountered in this book, such as the ferromagnetic, antiferromagnetic, nematic or superconducting phases. On varying the temperature, pressure and chemical potential(s) of a system, properties such as its structure, density, composition, compressibility, specific heat, etc., in general change smoothly. Yet under certain conditions the changes may be abrupt – some of these properties may exhibit discontinuities, or even divergences, at a phase transition . Phase transitions are among the most spectacular phenomena of nature. Consider, for instance, the phase sequence of water on heating: from ice, an opaque, slippery, rock-like solid; to colourless, incompressible, liquid water, which nevertheless easily flows under gravity; to water vapour, an invisible and very low-density (greenhouse!) gas, hence of ill-defined volume.
Phase, as the term is used in thermodynamics, refers to a spatially uniform equilibrium system. Substances undergo phase transitions, changes in phase that occur upon variations of state variables. The chemical potential of substances in coexisting phases has the same value in each of the phases in which coexistence occurs. The specific heat is discontinuous at the van der Waals critical point—a second-order phase transition in the Ehrenfest classification scheme. This chapter shows that one-dimensional systems cannot support phase transitions. Just as with liquid-vapor phase transitions, exponents characterize the critical behavior of magnetic systems. Magnets and fluids are different physical systems, yet they have the same critical behavior. Through the concept of order parameter, Landau theory subsumes the phase-transition behavior of different systems into one theory. A more physical way of demonstrating the existence of a phase transition would be to calculate the order parameter.
This chapter describes the physics of phase transitions and critical phenomena. After introducing the thermodynamics of phase transitions, the general considerations are made explicit by presenting statistical mechanical calculations on a lattice gas model in the mean-field approximation. Phase transitions occur in macroscopic systems when one or more external parameters like temperature, pressure, electrical field, magnetic field, etc are varied. The chapter demonstrates the utility of the alternative formulations of thermodynamics and statistical mechanics in the context of phase transitions and shows how their use clarifies and unifies the theory of phase transitions. It deals with the basic thermodynamic description of a single component fluid. To understand different phases and associated transitions, one studies how the couplings flow in the parameter space under repeated Renormalization Group (RG) transformations. The flows around the fixed point are easily studied by linearizing the RG equations around the fixed points and determining the eigenvalues and eigenvectors of the linearized RG transformations.
Originally, the term ‘dynamic critical phenomena’ was coined for time-dependent properties near second-order phase transitions in thermal equilibrium . The kinetics of phase transitions in magnets, at the gas–liquid transition, and at the normal- to superfluid phase transition in helium 4 were among the prominent examples investigated already in the 1960s. The dynamic scaling hypothesis , generalizing the scaling ansatz for the static correlation function and introducing an additional dynamic critical exponent, successfully described a variety of these experiments. Yet only the development of the systematic renormalization group (RG) approach for critical phenomena in the subsequent decade provided a solid conceptual foundation for phenomenological scaling theories. Supplemented with exact solutions for certain idealized model systems, and guided by invaluable input from computer simulations in addition to experimental data, the renormalization group now provides a general framework to explore not only the static and dynamic properties near a critical point, but also the large-scale and low-frequency response in stable thermodynamic phases. Scaling concepts and the renormalization group have also been successfully applied to phase transitions at zero temperature driven by quantum rather than thermal fluctuations. It is to be hoped that RG methods may help to classify the strikingly rich phenomena encountered in far-from-equilibrium systems as well. Recent advances in studies of simple reaction-diffusion systems, active to absorbing state phase transitions, driven lattice gases, and scaling properties of moving interfaces and growing surfaces, among others, appear promising in this respect.
Among the many applications of statistical mechanics, some of the most intriguing and challenging theoretical problems arise in connection with phase transitions. These are abrupt changes of state such as occur, for example, when a liquid is transformed into a vapour, a ferromagnet loses its magnetization upon heating to its Curie temperature, or at the onset at sufficiently low temperatures of superfluidity or superconductivity. It is within the theory of phase transitions, too, that the mathematical relationships between statistical mechanics and relativistic field theories are most powerful. Indeed, the idea of spontaneous symmetry breaking, which lies at the heart of the theory of phase transitions, is the crucial ingredient that turns the gauge theories of chapter 8 into a real working model of the fundamental forces of nature, to be discussed in the next chapter.
Aim and Scope of this Book A plethora of systems exhibit phase transitions as the temperature or some other parameter is changed. Examples range from the ice-water phase transition observed in our daily life to the loss of ferromagnetism in iron or to the more sophisticated Mott insulator-superfluid phase transition observed in optical lattices [343]. The last five decades have witnessed a tremendous upsurge in the studies of phase transitions at finite temperature [727, 149, 333, 136, 494, 541, 556]. The success of Landau-Ginzburg theories and the concepts of spontaneous symmetry breaking and the renormalization group [27, 410, 821, 578] in explaining many of the finite temperature phase transitions occurring in nature has been spectacular. In this book, we will consider only a subclass of phase transitions called quantum phase transitions (QPTs) [154, 658, 725, 799, 185, 63, 62, 66, 141, 744] and we will discuss these mainly from the view point of recent studies of information and dynamics. QPTs are zero temperature phase transitions which are driven by quantum fluctuations and are usually associated with a non-analyticity in the ground state energy density of a quantum many-body Hamiltonian. We will focus on continuous QPTs where the order parameter vanishes continuously at the quantum critical point (QCP) at some value of the parameters which characterize the Hamiltonian. We will not discuss first order quantum phase transitions associated with an abrupt change in the order parameter. Usually, a first order phase transition is characterized by a finite discontinuity in the first derivative of the ground state energy density. A continuous QPT is similarly characterized by a finite discontinuity, or divergence, in the second derivative of the ground state energy density, assuming that the first derivative is continuous. This is of course the classical definition; we will later mention some QPTs where the ground state energy density is not necessarily singular.
Among the many applications of statistical mechanics, some of the most intriguing and challenging theoretical problems arise in connection with phase transitions. These are abrupt changes of state such as occur, for example, when a liquid is transformed into a vapour, a ferromagnet loses its magnetization upon heating to its Curie temperature, or at the onset at suciently low temperatures of super uidity or superconductivity. It is within the theory of phase transitions, too, that the mathematical relationships between statistical mechanics and relativistic eld theories are most powerful. Indeed, the idea of spontaneous symmetry breaking, which lies at the heart of the theory of phase transitions, is the crucial ingredient that turns the gauge theories of Chapter 8 into a real working model of the fundamental forces of nature, to be discussed in the next chapter.