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CRC Press eBooks

The Grand Canonical Ensemble

Jonathan Allday, Simon Hands

Published Sep 3, 2024• 0 citations
Publisher

Abstract

We developed a reasonably detailed and comprehensive understanding of boson and fermion statistics from the previous chapter. While this is interesting physics in itself, more important for us is an understand of how the symmetry properties of these particles impact on the entropy associated with them. In this chapter, we start by considering situations where the number of particles in a system is not fixed. Next, the theory developed is used to derive quantum statistics again, but this time without recourse to various approximations. Access to the requisite probability functions enables the Gibbs entropy to be calculated for fermions and bosons .

DOI
10.1201/9781003121053-12

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We developed a reasonably detailed and comprehensive understanding of boson and fermion statistics from the previous chapter. While this is interesting physics in itself, more important for us is an understand of how the symmetry properties of these particles impact on the entropy associated with them. In this chapter, we start by considering situations where the number of particles in a system is not fixed. Next, the theory developed is used to derive quantum statistics again, but this time without recourse to various approximations. Access to the requisite probability functions enables the Gibbs entropy to be calculated for fermions and bosons .
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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
This chapter investigates a quantum gas in the grand-canonical ensemble with the grand canonical Hamiltonian ensemble. The path integral formalism pioneered by Feynman has proven to be an extremely useful tool for understanding and handling quantum mechanics, quantum field theory, and statistical mechanics. The path integral approach is a powerful tool that considers nonperturbative calculations for the investigation of many-particle systems. It is worth noting that while the path integral approach seems to be quite cumbersome in quantum mechanics, it does provide a powerful tool in quantum field theory. The entire aforementioned derivation is calculated in order to justify the evaluation of the path integral at equal times. The chapter examines the example of an atomic Fermi gas by considering an electron gas. The Fermi liquid concept is the deviation of the electron gas from the ideal gas behavior. It utilizes the so-called diagram technique to calculate some quantities.
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.
Abstract Chapter 6 introduces quantum-mechanical ensemble theory by proving the asymptotic equivalence of the quantum-mechanical, microcanonical ensemble average with the quantum grand canonical ensemble average for many-particle systems, based on the method of Darwin and Fowler. The procedures involved identify the grand partition function, entropy and other statistical thermodynamic variables, including the grand potential, Helmholtz free energy, thermodynamic potential, Gibbs free energy, Enthalpy and their relations in accordance with the fundamental laws of thermodynamics. Accompanying saddle-point integrations define temperature (inverse thermal energy) and chemical potential (Fermi energy). The concomitant emergence of quantum statistical mechanics and Bose–Einstein and Fermi–Dirac distribution functions are discussed in detail (including Bose condensation). The magnetic moment is derived from the Helmholtz free energy and is expressed in terms of a one-particle retarded Green’s function with an imaginary time argument related to inverse thermal energy. This is employed in a discussion of diamagnetism and the de Haas-van Alphen effect.
This chapter introduces the quantum mechanical canonical ensemble, which is used for the majority of problems in quantum statistical mechanics. The ensemble is derived and analogies with the classical ensemble are presented. A useful expression for the quantum entropy is derived. The origin of the Third Law is explained. The relationship between fluctuations and derivatives found in classical statistical mechanics is shown to have counterparts in quantum statistical mechanics. The factorization of the partition function is re-introduced as the best trick in quantum statistical mechanics. Due to their importance in later chapters, basic calculations of the properties of two-level systems and simple harmonic oscillators are derived.