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Oxford University Press eBooks

Ideal Quantum Gases

Robert H. Swendsen

Published Dec 10, 2019• 0 citations
Publisher

Abstract

As a preliminary to discussing the properties of Bose–Einstein and Fermi–Dirac gases, this chapter presents the basic quantum equations that underlie both. The process of building N-body states from single-particle states is described, along with notation necessary to simplify the problem. The average number of particles in a given energy state and chemical potential is derived for fermions and bosons. Although all atoms are either bosons or fermions, and therefore indistinguishable, there are nevertheless real systems that are composed of distinguishable particles. Although all atoms are either bosons or fermions, and therefore indistinguishable, there are nevertheless real systems that are composed of distinguishable particles.

DOI
10.1093/oso/9780198853237.003.0027

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As a preliminary to discussing the properties of Bose–Einstein and Fermi–Dirac gases, this chapter presents the basic quantum equations that underlie both. The process of building N-body states from single-particle states is described, along with notation necessary to simplify the problem. The average number of particles in a given energy state and chemical potential is derived for fermions and bosons. Although all atoms are either bosons or fermions, and therefore indistinguishable, there are nevertheless real systems that are composed of distinguishable particles. Although all atoms are either bosons or fermions, and therefore indistinguishable, there are nevertheless real systems that are composed of distinguishable particles.
This chapter develops the basic equations that will be used to analyse the Fermi-Dirac and Bose-Einstein gases. The representation of many-particle states in terms of products of single-particle states is presented. The reasons for using the quantum grand canonical ensemble are given, and a general expression for the grand canonical partition function is derived. The essential equations for fermions, bosons, and distinguishable particles are developed, and the basic strategy for using them to solve problems is given.
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
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 properties of the ideal Bose gas are calculated from the integral equations for the energy and the number of particles as a function of the temperature and chemical potential. It is shown that the integral equations break down below the Einstein temperature that corresponds to the transition to the low-temperature state. The lowest single-particle energy level must be treated explicitly to get the proper equations. With the inclusion of the lowest single-particle energy level, the low-temperature behavior is calculated. The occupation of the lowest level becomes comparable to the total number of particles in the system below the Einstein temperature, and equal to the total number of particles at zero temperature. A numerical solution to the properties of the Bose gas is discussed, and the detailed calculations are assigned to the problems at the end of the chapter.
Calculations of chemical potentials for ideal monatomic gases with Bose-Einstein and Fermi-Dirac statistics as functions of temperature, across the temperature region that is typical for the collective quantum degeneracy effect, are presented. Numerical calculations are performed without any additional approximations, and explicit dependences of the chemical potentials on temperature are constructed at a fixed density of gas particles. Approximate polynomial dependences of chemical potentials on temperature are obtained that allow for the results to be used in further studies without re-applying the involved numerical methods. The ease of using the obtained representations is demonstrated on examples of deformation of distribution for a population of energy states at low temperatures, and on the impact of quantum statistics (exchange interaction) on the equations of state for ideal gases and some of the thermodynamic properties thereof. The results of this study essentially unify two opposite limiting cases in an intermediate region that are used to describe the equilibrium states of ideal gases, which are well known from university courses on statistical physics, thus adding value from an educational point of view.