Overview Classical Statistical Mechanics (CSM) ignores the quantum nature of particles. This introduces three errors in the calculation of the partition function. First is the assumption of distinguishability of individual particles not possible in the microscopic world. Second, CSM neglects the discrete nature of system’s energy levels. Third, CSM fails to account for the spin of the particles which divides all particles into two types: boson and fermion, each following its own law of statistical distribution among energy levels. While CSM is impressively successful in describing observed properties of many naturally occurring large scale phenomena (particularly in liquids and biological systems), it fails to describe many phenomena where quantum nature of particles and quantum statistics play important role in determining properties such as electrical and thermal conductivity (particularly in solid materials) and superfluidity in liquid helium. It is not just at low temperatures where quantum nature is important, but also when the particle is intrinsically quantum, such as an electron. Quantum Statistical Mechanics (QSM) is also needed to understand biochemical reactions, like enzyme kinetics and optical properties of DNA. In this chapter, we discuss elementary aspects of quantum Statistical Mechanics, with detailed treatment of ideal Bose gas, leading to Bose-Einstein condensation.
Overview Classical Statistical Mechanics (CSM) ignores the quantum nature of particles. This introduces three errors in the calculation of the partition function. First is the assumption of distinguishability of individual particles not possible in the microscopic world. Second, CSM neglects the discrete nature of system’s energy levels. Third, CSM fails to account for the spin of the particles which divides all particles into two types: boson and fermion, each following its own law of statistical distribution among energy levels. While CSM is impressively successful in describing observed properties of many naturally occurring large scale phenomena (particularly in liquids and biological systems), it fails to describe many phenomena where quantum nature of particles and quantum statistics play important role in determining properties such as electrical and thermal conductivity (particularly in solid materials) and superfluidity in liquid helium. It is not just at low temperatures where quantum nature is important, but also when the particle is intrinsically quantum, such as an electron. Quantum Statistical Mechanics (QSM) is also needed to understand biochemical reactions, like enzyme kinetics and optical properties of DNA. In this chapter, we discuss elementary aspects of quantum Statistical Mechanics, with detailed treatment of ideal Bose gas, leading to Bose-Einstein condensation.
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 condensation, superfluidity, and superconductivity are quantum mechanics made visible. They mark the boundary between the classical and the quantum worlds, and they show the macroscopic role of quantum mechanics in condensed matter. This book presents these phenomena in terms of particles, their positions, and their momenta, giving a concrete visualisation and description that is not possible with traditional wave functions. A single approach that bridges the classical-quantum divide provides new insight into the role of particle interactions in condensation, the nature of collisions in superfluid flow, and the physical form of Cooper pairs in high-temperature superconductors. High-temperature superconductivity is explored with quantum statistical mechanics, which links it to Bose-Einstein condensation. Identifying a new mechanism for Cooper pairing, this explains the differences between the low- and high-temperature superconducting regimes and the role of the molecular structure of the conductor. The new perspective offered by this book on Bose-Einstein condensation, superfluidity, and high-temperature superconductivity gives particle-based explanations as well as mathematical and computational methods for these macroscopic quantum phenomena so that readers understand the role of particle interactions and structure in the physics of these phenomena. This book will appeal to undergraduate and graduate students, lecturers, academics, and scientific researchers in the fields of Bose-Einstein condensation and condensates, superfluidity, and superconductivity. It will also be of interest to those working with thermodynamics, statistical mechanics, statistical physics, quantum mechanics, molecular dynamics, materials science, condensed matter physics, and theoretical chemistry. Key Features: · Explores Bose-Einstein condensation with new evidence for multiple condensed states and novel Monte Carlo simulations for interacting bosons · Establishes the thermodynamic nature of condensed bosons from an analysis of fountain pressure measurements, including that they carry energy and entropy, and the thermodynamic principle of superfluid flow · Derives equations of motion for condensed bosons, and performs molecular dynamics simulations of the viscosity with molecular trajectories that give rise to superfluidity · Identifies the mechanism for electron pairing in high-temperature superconductivity
The topic of Bose–Einstein condensation in a uniform, non-interacting gas of bosons is treated in most textbooks on statistical mechanics. In the present chapter we discuss the properties of a non-interacting Bose gas in a trap. We shall calculate equilibrium properties of systems in a semi-classical approximation, in which the energy spectrum is treated as a continuum. For this approach to be valid the temperature must be large compared with Δ∈/ k , where Δ∈ denotes the separation between neighbouring energy levels. As is well known, at temperatures below the Bose–Einstein condensation temperature, the lowest energy state is not properly accounted for if one simply replaces sums by integrals, and it must be included explicitly. The statistical distribution function is discussed in Sec. 2.1, as is the single-particle density of states, which is a key ingredient in the calculations of thermo dynamic properties. Calculations of the transition temperature and the fraction of particles in the condensate are described in Sec. 2.2. In Sec. 2.3 the semi-classical distribution function is introduced, and from this we determine the density profile and the velocity distribution of particles. Thermodynamic properties of Bose gases are calculated as functions of the temperature in Sec. 2.4. The final two sections are devoted to effects not captured by the simplest version of the semi-classical approximation: corrections to the transition temperature due to a finite particle number (Sec. 2.5), and thermodynamic properties of gases in lower dimensions (Sec. 2.6).
The topic of Bose–Einstein condensation in a uniform, non-interacting gas of bosons is treated in most textbooks on statistical mechanics. In the present chapter we discuss the properties of a non-interacting Bose gas in a trap. We shall calculate equilibrium properties of systems in a semi-classical approximation, in which the energy spectrum is treated as a continuum. For this approach to be valid the temperature must be large compared with Δ∊/ k , where Δ∊ denotes the separation between neighbouring energy levels. As is well known, at temperatures below the Bose–Einstein condensation temperature, the lowest-energy state is not properly accounted for if one simply replaces sums by integrals, and it must be included explicitly. The statistical distribution function is discussed in Sec. 2.1, as is the single-particle density of states, which is a key ingredient in the calculations of thermodynamic properties. Calculations of the transition temperature and the fraction of particles in the condensate are described in Sec. 2.2. In Sec. 2.3 the semi-classical distribution function is introduced. From this we obtain the density profile and the velocity distribution of particles, and use these to determine the shape of an anisotropic cloud after free expansion. Thermodynamic properties of Bose gases are calculated as functions of the temperature in Sec. 2.4. Finally, Sec. 2.5 treats corrections to the transition temperature due to a finite particle number.
Classical statistical mechanics tries to derive the macroscopic properties of matter starting from the mechanical laws that rule the behaviour of single particles. To describe equilibrium states, only observables accounting for correlations among states are considered, and only systems consisting of a large number of particles are taken into account. The observables are described by continuous functions on phase space, and the states are represented by linear assignments of a number to each observable. Within the framework of the canonical ensemble, one deals with mechanical systems in thermal equilibrium with a thermal reservoir, and the equilibrium state is reached as a result of the interaction with the external world. The external world may be really external, or equally well, the unrecognized internal degrees of freedom, like in the calculation of viscosity or thermal conductivity. If really only the external world is the cause we may expect some surface dependence while an internal unrecognized degree of freedom would have a volume effect, unless the interactions are long range. The microcanonical ensemble is instead introduced to study isolated mechanical systems, and the equilibrium is viewed as a temporal average, rather than as a limit. Attention is then focused on partition functions, the theorem of equipartition of energy and an elementary theory of specific heats. In the second part, the Planck derivation of the law of black-body radiation is analysed, presenting in chronological order the Kirchhoff theorem, the Stefan law, the Wien displacement law, the Rayleigh–Jeans formula and the Planck hypothesis. Further topics discussed are the Einstein and Debye quantum models for specific heats of solids. These topics prepare the ground for the introduction of quantum statistical mechanics. The third part is, in fact, devoted to the analysis of identical particles in quantum mechanics.
Thermodynamics is used to describe the bulk properties of matter in or near equilibrium. Many scientists, notably Boyle, Carnot, Clausius, Gay-Lussac, Gibbs, Joule, Kelvin, and Rumford, contributed to the development of the field over three centuries. Quantities such as mass, pressure, energy, and so on are readily defined and measured. Classical statistical mechanics attempts to understand thermodynamics by the application of classical mechanics to the microscopic particles making up the system. Great progress in this field was made by physicists like Boltzmann and Maxwell. Temperature, entropy, particle number, and chemical potential are thus understandable in terms of the microscopic nature of matter. Classical mechanics is inadequate in many circumstances however, and ultimately must be replaced by quantum mechanics. In fact, the ultraviolet catastrophe encountered by the application of classical mechanics and electromagnetism to blackbody radiation was one of the problems that led to the development of quantum theory. The development of quantum statistical mechanics was achieved by a number of twentieth century physicists, most notably Planck, Einstein, Fermi, and Bose. The purpose of this chapter is to give a mini-review of the basic concepts of quantum statistical mechanics as applied to noninteracting systems of particles. This will set the stage for the functional integral representation of the partition function, which is a cornerstone of modern relativistic quantum field theory and the quantum statistical mechanics of interacting particles and fields. Ensembles One normally encounters three types of ensemble in equilibrium statistical mechanics. The microcanonical ensemble is used to describe an isolated system that has a fixed energy E , a fixed particle number N , and a fixed volume V .