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.
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.
The statistical properties of non-interacting bosons and fermions confined in trapping potentials are most easily obtained when the system may exchange energy and particles with a large reservoir (grand-canonical ensemble). There are circumstances, however, where the system under consideration may be considered as being isolated (micro-canonical ensemble). This paper first reviews results relating to micro-canonical ensembles. Some of them were obtained a long time ago, particularly by Khinchin in 1950. Others were obtained only recently, often motivated by experimental results relating to atomic confinement. A number of formulas are reported for the first time in the present paper. Formulas applicable to the case where the system may exchange energy but not particles with a reservoir (canonical ensemble) are derived from the micro-canonical ensemble expressions. The differences between the three ensembles tend to vanish in the so-called Thermodynamics limit, that is, when the number of particles and the volume go to infinity while the particle number density remains constant. But we are mostly interested in systems of moderate size, often referred to as being mesoscopic, where the grand-canonical formalism is not applicable. The mathematical results rest primarily on the enumeration of partitions of numbers.
Equilibrium distribution functions are obtained for boson and fermion ensembles with a limited number of particles. It is shown that the number-of-particle distribution functions in different quantum states are statistically dependent; this dependence disappears only for a large number of particles in the ensemble. The distributions are transformed into the Boltzmann distribution at a high temperature and into the Bose-Einstein and Fermi-Dirac distributions for a large number of particles in the ensemble.
We derive an expression for the reduced density matrices of ideal Bose and Fermi gases in the canonical ensemble, which corresponds to the Bloch--De Dominicis (or Wick's) theorem in the grand canonical ensemble for normal-ordered products of operators. Using this expression, we study one- and two-body correlations of homogeneous ideal gases with
N particles. The pair distribution function
g(2)(r) of fermions clearly exhibits antibunching with
g(2)(0)=0 due to the Pauli exclusion principle at all temperatures, whereas that of normal bosons shows bunching with
g(2)(0)≈2, corresponding to the Hanbury Brown--Twiss effect. For bosons below the Bose--Einstein condensation temperature
T0, an off-diagonal long-range order develops in the one-particle density matrix to reach
g(1)(r)=1 at
T=0, and the pair correlation starts to decrease towards
g(2)(r)≈1 at
T=0. The results for
N→∞ are seen to converge to those of the grand canonical ensemble obtained by assuming the average
⟨ψ^(r)⟩ of the field operator
ψ^(r) below
T0. This fact justifies the introduction of the "anomalous" average
⟨ψ^(r)⟩=0 below
T0 in the grand canonical ensemble as a mathematical means of removing unphysical particle-number fluctuations to reproduce the canonical results in the thermodynamic limit.