In Chapter 3, we examined two examples of phase transitions, the paramagnetic–ferromagnetic transition (Section 3.1.4) and the liquid–vapour transition (Section 3.5.4). In the latter case, thermodynamic functions such as entropy or specific volume are discontinuous at the transition. When, for example, one varies the temperature T at constant pressure, the transition takes place at a temperature T c where the Gibbs potentials of the two phases are equal, but the two phases coexist at T c and are either stable or metastable in the vicinity of T c . Each of the phases carries with it its own entropy, specific volume, etc., which are in general different at T = T c , hence the discontinuities. Such a phase transition is called a first order phase transition . The picture is quite different in the paramagnetic–ferromagnetic phase transition: the thermodynamic quantities are continuous at the transition, the transition is not linked to the crossing of two thermodynamic potentials and one never observes metastability. Such a transition is called a second order, or continuous, phase transition . The transition temperature is called the critical temperature and is denoted by T c . The new and remarkable feature which we shall encounter in continuous phase transitions is the existence of cooperative phenomena. To be specific, think of a spin system, for example an Ising or a Heisenberg model, where the interactions between spins are limited to nearest neighbours. More generally we shall consider short range interactions , which decrease rapidly as a function of the distance between spins, and we exclude from our study all long range interactions.
In Chapter 3, we examined two examples of phase transitions, the paramagnetic–ferromagnetic transition (Section 3.1.4) and the liquid–vapour transition (Section 3.5.4). In the latter case, thermodynamic functions such as entropy or specific volume are discontinuous at the transition. When, for example, one varies the temperature T at constant pressure, the transition takes place at a temperature T c where the Gibbs potentials of the two phases are equal, but the two phases coexist at T c and are either stable or metastable in the vicinity of T c . Each of the phases carries with it its own entropy, specific volume, etc., which are in general different at T = T c , hence the discontinuities. Such a phase transition is called a first order phase transition . The picture is quite different in the paramagnetic–ferromagnetic phase transition: the thermodynamic quantities are continuous at the transition, the transition is not linked to the crossing of two thermodynamic potentials and one never observes metastability. Such a transition is called a second order, or continuous, phase transition . The transition temperature is called the critical temperature and is denoted by T c . The new and remarkable feature which we shall encounter in continuous phase transitions is the existence of cooperative phenomena. To be specific, think of a spin system, for example an Ising or a Heisenberg model, where the interactions between spins are limited to nearest neighbours. More generally we shall consider short range interactions , which decrease rapidly as a function of the distance between spins, and we exclude from our study all long range interactions.
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 transitions are defined, and the concepts of order parameter and spontaneously broken symmetry are discussed. Simple models for magnetic phase transitions are introduced, together with some experimental examples. Critical exponents and the notion of universality are defined, and the consequences of the scaling assumptions are derived. Phase transitions and order parameters It is a fact of everyday experience that matter in thermodynamic equilibrium exists in different macroscopic phases. Indeed, it is difficult to imagine life on Earth without all three phases of water. A typical sample of matter, for example, has the temperature–pressure phase diagram presented in Fig. 1.1: by changing either of the two parameters the system may be brought into a solid, liquid, or gas phase. The change of phase may be gradual or abrupt. In the latter case, the phase transition takes place at well defined values of the parameters that determine the phase boundary. Phase transitions are defined as points in the parameter space where the thermodynamic potential becomes non-analytic. Such a non-analyticity can arise only in the thermodynamic limit, when the size of the system is assumed to be infinite. In a finite system the partition function of any system is a finite sum of analytic functions of its parameters, and is therefore always analytic. A sharp phase transition is thus a mathematical idealization, albeit one that describes the reality extremely well. Macroscopic systems typically contain ∼ 10 23 degrees of freedom, and as such are very close to being in the thermodynamic limit. The phase boundaries in Fig. 1.1, for example, for this reason represent reproducible physical quantities.
Monte-Carlo simulation can be used to investigate cooperative phenomena, such as phase changes that occur when short-range atomic or molecular interactions give rise to long-range order. For example, some magnetic materials exhibit a paramagnetic phase at high temperatures, where the magnetic structure is disordered, but undergo a phase transition to a more ordered state at a lower temperature. This chapter uses a two-dimensional lattice Ising spin model, where spins on each site can be either up or down, to determine the critical temperature at which the phase transition occurs. In addition, it calculates the variation of energy, specific heat capacity, magnetisation and magnetic susceptibility with temperature. The chapter explains both the Gibbs and Metropolis sampling techniques, and lists a Python program that makes use of the latter.
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.
The standard Theory of Critical Phenomena within Boltzmann-Gibbs statistical mechanics is known to successfully predict, at any temperature differing from a continuous-phase-transition critical one, the (finite) values for thermodynamically relevant quantities such as isothermal magnetic susceptibility, specific heat, correlation length, Grüneisen parameter, and similar ones. However, at the precise critical point, empirically unreachable infinities emerge within that approach at the N→∞ thermodynamical limit. Such divergences, although mathematically correct, may be seen as poorly informative ones. Indeed, they make no distinction at all between say the Ising, XY, Heisenberg, and other models. Moreover, for say the XY model, they make no distinction whether the spins are, for instance, 1/2, 1 or 3/2, or whether the interactions are say first-neighbor or first-and-second-neighbor ones. The introduction of nonadditive entropic functionals within a consistently generalized statistical mechanics substantially improves the situation, i.e., it regularizes the theory providing informative finite values instead of mere infinities. This undoubtedly enriching fact is illustrated [Soares et al., Phys. Rev. B 111, L060409 (2025)] for the Grüneisen parameter at the zero-temperature quantum critical point of a spin-1/2 ferromagnetic Ising chain in the presence of a transverse magnetic field, by introducing the nonadditive entropic functional Sq with the unique value q=q⋆≡37-6=0.0828…, which precisely guarantees the thermodynamical extensivity of the entropy as mandated by the preservation of the Legendre-transform structure of classical thermodynamics.
A few paradigmatic one-dimensional lattice-statistical spin models have recently attracted a vigorous scientific interest owing to their peculiar thermodynamic behavior, which is highly reminiscent of a temperature-driven phase transition. The pseudotransitions of one-dimensional lattice-statistical spin models differ from actual phase transitions in several important aspects: the first-order derivatives of the Gibbs free energy such as entropy or magnetization exhibit near a pseudo-transition an abrupt continuous change instead of a true discontinuity, whereas the second-order derivatives of the Gibbs free energy such as specific heat or susceptibility display near a pseudo-transition a vigorous finite peak instead of an actual power-law divergence. In the present chapter we will comprehensively examine a pseudo-critical behavior of the spin-1/2 Ising diamond and tetrahedral chains by a detailed examination of basic magnetothermodynamic quantities such as the entropy, specific heat and susceptibility. It will be demonstrated that density plots of these magnetothermodynamic quantities provide a useful tool for establishing a finite-temperature diagram, which clearly delimits boundaries between individual quasi-phases in spite of a lack of true spontaneous long-range order at any nonzero temperature. It is suggested that a substantial difference between the degeneracies of two ground states of the spin-1/2 Ising diamond and tetrahedral chains is an essential prerequisite for observation of a relevant pseudo-critical behavior in a close vicinity of their ground-state phase boundary.