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Cambridge University Press eBooks

Quantum ideal gases

B. Widom

Published Apr 18, 2002• 0 citations
Publisher

Abstract

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.

DOI
10.1017/cbo9780511815836.009

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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.
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
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.
Why is it that particles with half-integer spin are Fermi particles whereas particles with integer spin are Bose particles? An explanation has been worked out by Pauli from complicated arguments from quantum field theory and relativity. He has shown that the two must necessarily go together … but we have not been able to reproduce his arguments on an elementary level. This probably means we do not have a complete understanding of the fundamental principle involved… R. P. Feynman, R.B. Leighton and M. Sands, Feynman Lectures on Physics , Volume 3, Chapter 4, Section 1, Addison-Wesley, Reading, MA (1963) Introduction Particles with half-integer angular momentum obey the Pauli exclusion principle (PEP) – a restriction that a non-degenerate single-particle quantum state can have occupation number of only 0 or 1. This restriction was announced by W. Pauli in 1924 for which, in 1945, he received the Nobel Prize in Physics. Soon after Pauli, the exclusion principle was generalized by P. Dirac and E. Fermi who – independently – integrated it into quantum mechanics. As a consequence half-integer spin particles are called Fermi–Dirac particles or fermions . PEP applies to electrons, protons, neutrons, neutrinos, quarks – and their antiparticles – as well as composite fermions such as He 3 atoms. Thermodynamic properties of metals and semiconductors are largely determined by electron (fermion) behavior.
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 laser cooling mechanisms described in Chapter 4 operate irrespective of the statistics of the atom, and they can therefore be used to cool Fermi species. The statistics of a neutral atom is determined by the number of neutrons in the nucleus, which must be odd for a fermionic atom. Since alkali atoms have odd atomic number Z , their fermionic isotopes have even mass number A . Such isotopes are relatively less abundant than those with odd A since they have both an unpaired neutron and an unpaired proton, which increases their energy by virtue of the odd–even effect. In early experiments, 40 K and 6 Li atoms were cooled to about one-quarter of the Fermi temperature. More recently, fermionic alkali atoms have been cooled to temperatures well below one-tenth of their Fermi temperature, and in addition a degenerate gas of the fermionic species 173 Yb (with I = 5/2) has been prepared. In the classical limit, at low densities and/or high temperatures, clouds of fermions and bosons behave alike. The factor governing the importance of quantum degeneracy is the phase-space density ϖ introduced in Eq. (2.24), and in the classical limit ϖ ≪ 1. When ϖ becomes comparable with unity, gases become degenerate: bosons condense in the lowest single-particle state, while fermions tend towards a state with a filled Fermi sea. As one would expect on dimensional grounds, the degeneracy temperature for fermions – the Fermi temperature T F – is given by the same expression as the Bose–Einstein transition temperature for bosons, apart from a numerical factor of order unity.
In quantum mechanics, elementary particles of the same type are considered identical. For example, an electron in an atom could be replaced by another electron and the atom would behave in exactly the same way. Nature has taken particular advantage of this, allowing only two types of elementary particles: bosons and fermions. They differ fundamentally in how a collection of identical particles interact. Identical fermions cannot occupy the same quantum state (only one per state!). Identical bosons can occupy the same quantum state. The statistics of identical particles (how they act in groups) has profound affects. For example, the rich and complex structure of the periodic table arises from the principle that only one electron can occupy each quantum state. The spin and the statistics of particles are closely connected: (fermions) bosons have (half-)integer spin. (Spin is an internal angular momentum measured in units of Planck’s constant.)