Abstract This chapter first discusses the quantum mechanics of non-interacting electrons in a box. The simplest model of a metal is to assume it consists of free electrons in a box, with their mutual Coulomb repulsion ‘switched off’. The atoms in these materials (Li, Na, K, Rb, and Cs) have low ionization energies, only weakly binding their single valence s electron to the nucleus. It can then be imagined that when assembled as a crystal, each atom contributes one valence electron to the formation of a kind of electron gas or quantum plasma having a number density equal to that of the atoms. On average, the nuclear charge will compensate the free or mobile electronic charge. The remainder of the chapter covers Fermi–Dirac statistics; evaluation of integrals involving the Fermi distribution function; the temperature dependence of the chemical potential; energy of an ideal Fermi gas as a function of temperature; the paramagnetic susceptibility of a Fermi gas; and a qualitative discussion of the behaviour of a Fermi gas. Sample problems are also provided at the end of the chapter.
Abstract This chapter first discusses the quantum mechanics of non-interacting electrons in a box. The simplest model of a metal is to assume it consists of free electrons in a box, with their mutual Coulomb repulsion ‘switched off’. The atoms in these materials (Li, Na, K, Rb, and Cs) have low ionization energies, only weakly binding their single valence s electron to the nucleus. It can then be imagined that when assembled as a crystal, each atom contributes one valence electron to the formation of a kind of electron gas or quantum plasma having a number density equal to that of the atoms. On average, the nuclear charge will compensate the free or mobile electronic charge. The remainder of the chapter covers Fermi–Dirac statistics; evaluation of integrals involving the Fermi distribution function; the temperature dependence of the chemical potential; energy of an ideal Fermi gas as a function of temperature; the paramagnetic susceptibility of a Fermi gas; and a qualitative discussion of the behaviour of a Fermi gas. Sample problems are also provided at the end of the chapter.
Bose–Einstein and Fermi–Dirac statistics versus Boltzmann statistics It was remarked in Chapter 2, §2.1, that there are circumstances in which the “Boltzmann statistics” for an ideal gas – the approximation in Eq. (2.6), in which the total partition function is decomposed into a product of single-molecule partition functions, with division by N 1 ! N 2 ! … to correct for particle identity – is inaccurate even if the gas is still ideal (non-interacting particles). That happens when the number of single-particle states within the energy kT of the ground state is no longer very much greater than the number of particles. (Recall Fig. 2.1 and the accompanying discussion.) We noted that when the Boltzmann statistics is no longer an adequate approximation one must distinguish the particles as fermions, no two of which can be in the same single-particle state (counting states of different spin as different), or as bosons, for which there is no restriction on multiple occupancy of the singleparticle states. Fermions are particles of half-odd-integer spin quantum number; they could be composite particles consisting of an odd number of spin-½ particles. Protons, neutrons, and electrons, all of which are of spin ½, are fermions. Bosons are particles of integer spin; they could be spinless, or of spin 1, etc., or could be composites consisting of an even number of fermions. The nuclei of helium atoms of mass number 4 consist of two protons and two neutrons, and the neutral atom has two electrons outside the nucleus; 4 He atoms are bosons.
The art of being wise is the art of knowing what to overlook. William James Summary This chapter is devoted to idealized models and theoretical concepts that underlie the topics in the rest of this book. Among the most dramatic effects are the Wigner and Mott transitions, exemplified by electrons in a homogeneous background of positive charge and by the Hubbard model of a crystal. Fermi liquid theory is the paradigm for understanding quasi-particles and collective excitations in metals, building on a continuous link between a non-interacting and an interacting system. The Luttinger theorem and Friedel sum rule are conservation laws for quantities that do not vary at all with the interaction. The Heisenberg and Ising models exemplify the properties of localized electronic states that act as spins. The Anderson impurity model is the paradigm for understanding local moment behavior and is used directly in dynamical mean-field theory. The previous chapters discuss examples of experimental observations where effects of interactions can be appreciated with only basic knowledge of physics and chemistry. The purpose of this chapter is to give a concise discussion of models that illustrate major characteristics of interacting electrons. These are prototypes that bring out features that occur in real problems, such as the examples in the previous chapter. They are also pedagogical examples for the theoretical methods developed later, with references to specific sections. The Wigner transition and the homogeneous electron system The simplest model of interacting electrons in condensed matter is the homogeneous electron system, also called homogeneous electron gas (HEG), an infinite system of electrons with a uniform compensating positive charge background. It was originally introduced as a model for alkali metals. Now the HEG is a standard model system for the development of density functionals and a widely used test system for the many-body perturbation methods in Chs. 10–15. It is also an important model for quantum Monte Carlo calculations, described in Chs. 23–25. To define the model, we take the hamiltonian in Eq. (1.1) and replace the nuclei by a rigid uniform positive charge with density equal to the electron charge density n .
Abstract Chapter 11 presents a statistical mechanical treatment of the quantum ideal gases, i.e., the ideal Boltzmann, fermion, and boson gases. The discussion begins with the microscopic description and the solution of the eigenvalue problem for a quantum ideal gas. It is argued that calculating the partition function is most readily accomplished in the grand canonical ensemble using a second-quantized formulation. When the particles are distinguishable, the equation of state is identical to that of a classical ideal gas. For fermions and bosons, however, the problem of computing thermodynamic properties is significantly more complex and can only be solved exactly in certain limits. Away from these limits approximations are needed and are discussed in detail. The relevant distributions - the Fermi-Dirac and Bose-Einstein distributions are derived. The local density approximation of density functional theory is derived for the ideal electron gas. For the ideal boson gas, the phenomenon of Bose-Einstein condensation is discussed
Introduction In this chapter we study metal–insulator transitions which occur due to correlations between the charge carriers. This quantum phase transitions results from the competition between kinetic energy and Coulomb repulsion where the latter has the tendency to localise the electrons. The simplest model which describes this competition is the one-band Hubbard model with its two energy scales, the bandwidth W and the Coulomb repulsion U between electrons of opposite spins on the same site. For a fixed density of electrons, n = 1; as the ratio U/W increases, we expect to find a zero-temperature phase transition from a metallic state to an insulator where the electrons are frozen at the lattice sites. The method employed here to investigate this transition is the Gutzwiller approach (Gutzwiller, 1965). This is a variational method which played an important role in providing a framework for the ideas of Mott on the problem of the metal–insulator transition (Mott, 1974). On the metallic side of the transition, this approach describes a metal with renormalised Fermi liquid parameters, essentially with enhanced effective mass and uniform susceptibility. This is the so-called highly correlated electron gas (Brinkman and Rice, 1970) for which the metal oxide V 2 O 3 is the prototype system. In the insulating side, Gutzwiller's approximation yields a noninteracting system of localised electrons. This insulating phase is incompressible , i.e. has zero compressibility and infinite zero temperature susceptibility. The latter is not a consequence of interactions but simply due to the divergence of the Curie susceptibility, χ ∝ 1 /T , of non-interacting moments at T = 0. Then, in Gutzwiller's approach the transition is from a paramagnetic metal to a paramagnetic insulator. We will continue using the designation Mott transition to describe this type of phase transition where the insulating phase has no long-range magnetic order. In real systems, most frequently, localisation due to interactions is accompanied by the appearance of antiferromagnetic order.
This chapter considers the interactions between the constituents of say a metal, i.e., electrons and ions. By adopting a mean field approach, the dynamics of the electrons can be obtained by perturbation theory from the properties of the non-interacting electrons, and the effective electron-electron interaction in good conductors is considered. Electron diffraction or X-ray experiments reveal the grainy character of a metal. Charge is separated spatially into two pieces: the nuclei and the tightly bound electrons, and the conduction electrons, which have their density spread throughout the solid. The mean field Hamiltonian is specified in terms of the mean field, which in turn is specified in terms of the average charge density. The diagrammatic interpretation of the degenerate free Fermi gas density response function allows us also to get a diagrammatic interpretation of the interacting Fermi gas density response function.
Fermionic matter is ubiquitous in nature, from the electrons in metals and semiconductors or the neutrons in the inner crust of neutron stars, to gases of fermionic atoms, like 40K or 6Li that can be created and studied under laboratory conditions. It is especially interesting to study these systems at very low temperatures, where we enter the world of quantum mechanical phenomena. Due to the Fermi-Dirac statistics, a dilute system of spin-polarised fermions exhibits no interactions and can be viewed as an ideal Fermi gas. However, interactions play a crucial role for fermions of several spin species. This thesis addresses several questions concerning interacting Fermi gases, in particular the transition between the normal and the superfluid phase and dynamical properties at higher temperatures. First we will look at the unitary Fermi gas: a two-component system of fermions interacting with divergent scattering length. This system is particularly interesting as it exhibits universal behaviour. Due to the strong interactions perturbation theory is inapplicable and no exact theoretical description is available. I will describe the Determinant Diagrammatic Monte Carlo algorithm with which the unitary Fermi gas can be studied from first principles. This algorithm fails in the presence of a spin imbalance (unequal number of particles in the two components) due to a sign problem. I will show how to apply reweighting techniques to generalise the algorithm to the imbalanced case, and present results for the critical temperature and other thermodynamic observables at the critical point, namely the chemical potential, the energy per particle and the contact density. These are the first numerical results for the imbalanced unitary Fermi gas at finite temperature. I will also show how temperatures beyond the critical point can be accessed and present results for the equation of state and the temperature dependence of the contact density. At sufficiently high temperatures a semiclassical description captures all relevant physical features of the system. The dynamics of an interacting Fermi gas can then be studied via a numerical simulation of the Boltzmann equation. I will describe such a numerical setup and apply it to study the collision of two spin-polarised fermionic clouds. When the two components are separated in an elongated harmonic trap and then released, they collide and for sufficiently strong interactions can bounce off each other several times. I will discuss the different types of the qualitative behaviour, show how they can be interpreted in terms of the equilibrium properties of the system, and explain how they relate to the coupling between different excitation modes. I will also demonstrate how transport coefficients, for instance the spin drag, can be extracted from the numerical data.