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arXiv:1104.2611

Revisiting the concept of chemical potential in classical and quantum gases: A perspective from Equilibrium Statistical Mechanics

Francisco J. Sevilla, Luis Olivares‐Quiroz

Published Apr 13, 2011• 3 citations
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Abstract

In this work we revisit the concept of chemical potential $μ$ in both classical and quantum gases from a perspective of Equilibrium Statistical Mechanics (ESM). Two new results regarding the equation of state $μ=μ(n,T)$, where $n$ is the particle density and $T$ the absolute temperature, are given for the classical interacting gas and for the weakly-interacting quantum Bose gas. In order to make this review self-contained and adequate for a general reader we provide all the basic elements in an advanced-undergraduate or graduate statistical mechanics course required to follow all the calculations. We start by presenting a calculation of $μ(n,T)$ for the classical ideal gas in the canonical ensemble. After this, we consider the interactions between particles and compute the effects of them on $μ(n,T)$ for the van der Waals gas. For quantum gases we present an alternative approach to calculate the Bose-Einstein (BE) and Fermi-Dirac (FD) statistics. We show that this scheme can be straightforwardly generalized to determine what we have called Intermediate Quantum Statistics (IQS) which deal with ideal quantum systems where a single-particle energy can be occupied by at most $j$ particles with $0 \leqslant j \leqslant N$ with $N$ the total number of particles. In the final part we address general considerations that underlie the theory of weakly interacting quantum gases. In the case of the weakly interacting Bose gas, we focus our attention to the equation of state $μ=μ(n,T)$ in the Hartree-Fock mean-field approximation (HF) and the implications of such results in the elucidation of the order of the phase transitions involved in the BEC phase for non-ideal Bose gases.

DOI
10.48550/arxiv.1104.2611

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In this work we revisit the concept of chemical potential μμμ in both classical and quantum gases from a perspective of Equilibrium Statistical Mechanics (ESM). Two new results regarding the equation of state μ=μ(n,T)μ=μ(n,T)μ=μ(n,T), where nnn is the particle density and TTT the absolute temperature, are given for the classical interacting gas and for the weakly-interacting quantum Bose gas. In order to make this review self-contained and adequate for a general reader we provide all the basic elements in an advanced-undergraduate or graduate statistical mechanics course required to follow all the calculations. We start by presenting a calculation of μ(n,T)μ(n,T)μ(n,T) for the classical ideal gas in the canonical ensemble. After this, we consider the interactions between particles and compute the effects of them on μ(n,T)μ(n,T)μ(n,T) for the van der Waals gas. For quantum gases we present an alternative approach to calculate the Bose-Einstein (BE) and Fermi-Dirac (FD) statistics. We show that this scheme can be straightforwardly generalized to determine what we have called Intermediate Quantum Statistics (IQS) which deal with ideal quantum systems where a single-particle energy can be occupied by at most jjj particles with 0⩽j⩽N0 \leqslant j \leqslant N0⩽j⩽N with NNN the total number of particles. In the final part we address general considerations that underlie the theory of weakly interacting quantum gases. In the case of the weakly interacting Bose gas, we focus our attention to the equation of state μ=μ(n,T)μ=μ(n,T)μ=μ(n,T) in the Hartree-Fock mean-field approximation (HF) and the implications of such results in the elucidation of the order of the phase transitions involved in the BEC phase for non-ideal Bose gases.
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.
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
In this work, improvements are introduced to the current models of the ideal Fermi gas and the ideal Bose gas by incorporating the quantum nature of phase space, which is directly linked to the uncertainty principle. These improved models build upon the recently developed concepts of quantum phase space (QPS) and the QPS representation of quantum mechanics. The Hamiltonian operator for a gas particle and its eigenstates are first determined, and quantum statistical mechanics is used to derive the thermodynamic properties of the ideal gas. Analytic expressions for thermodynamic quantities—including the grand canonical potential, particle number, internal energy, von Neumann entropy, and pressure—are derived, along with the corresponding thermodynamic equations of state for both bosons and fermions. These corrections are particularly significant at low temperatures and in confined volumes, where quantum effects related to system geometry, such as shape and size, become significant. The results also establish a direct link between thermodynamic functions and the quantum statistical variances of momentum. Importantly, the improved models recover well-known classical relations of the ideal gas in the high-temperature and large-volume limits, ensuring consistency with classical physics. By addressing quantum corrections and their thermodynamic implications, this work provides a foundation for further applications in nanoscale systems, quantum gases, low-temperature physics, ultracold physics, and astrophysics.
Predictions from Hartree–Fock (HF), Popov (P), Yukalov–Yukalova (YY) and t -matrix approximations regarding the thermodynamics from the normal to the Bose–Einstein condensation (BEC) phase in weakly interacting Bose gases are considered. By analysing the dependence of the chemical potential μ on the temperature T and particle density ρ, we show that none of them predicts a second-order phase transition as required by symmetry-breaking general considerations. In this work, we find that the isothermal compressibility κ T predicted by these theories does not diverge at criticality as expected in a true second-order phase transition. Moreover, the isotherms μ = μ(ρ, T ) typically exhibit non-single-valued behaviour in the vicinity of the BEC transition, a feature forbidden by general thermodynamic principles. This behaviour can be avoided if a first-order phase transition is appealed. The facts described above show that although these mean field approximations give correct results near zero temperature, they are endowed with thermodynamic anomalies in the vicinity of the BEC transition. We address the implications of these results in the interpretation of current experiments with ultracold trapped alkali gases.
In a recent paper [Int. J. Mod. Phys. B 14, 405 (2000)] we discussed the Bose-Einstein condensation (BEC) in the framework of Tsallis’s nonextensive statistical mechanics. In particular, we studied an ideal gas of bosons in a confining harmonic potential. In this memoir we generalize our previous analysis by investigating an ideal Bose gas in a generic power-law external potential. We derive analytical formulas for the energy of the system, the BEC transition temperature and the condensed fraction. PACS numbers: 05.30-d; 03.75.Fi 1 Recently we analyzed the consequences of weak nonextensivity on Bose-Einstein Condensation for an ideal Bose gas 1 by using Tsallis’s nonextensive statistical mechanics (NSM). 2 From the nonextensive Bose-Einstein distribution 3−5 we derived the BEC transition temperature, the condensed fraction and the energy per particle in three different cases: the homogeneous gas, the gas in a harmonic trap and the relativistic homogenous gas. In this short contribution we generalize our previous results by considering the ideal Bose gas in a generic power-law potential. All the calculations are performed by assuming a D-dimensional space. The NSM predicts that, for an ideal quantum gas of identical bosons in the grand canonical ensemble, the weak nonextensivity formula of the average number of particles with energy ǫ is given by 〈n(ǫ)〉q = 1
In this paper, first of all, we proved if the ideal Bose gas with a finite volume and number of particles has a non-degenerate single-particle energy level n, the chemical potential μ can take the value μn = n and there is a phase transition temperature Tp,n, where n = 0,1,2 Taking 0 ≤ n Tp,n+1. When the temperature T > Tp,n or T ≤ Tp,n+1, μ # n and the most probable occupation number Nn = 0. In the temperature interval Tp,n ≥ T > Tp,n+1, μ = n and 0 ≤ Nn = N - NjsupNn, where Nj is the most probable occupation number in the degenerate level j. Thus, if the finite ideal Bose gas has some non-degenerate single-particle levels, there exists a characteristic temperature Tp = Tp,0. The chemical potential μ is quantized when T ≤ Tp, and this leads to the creation of a macroscopic quantum state (pure state) or Bose-Einstein condensation phase. Tp = Tp,0 is a first-order phase transition point, Tp,n#0 is a zero-order phase transition point. Next, we obtained a new expression of the most probable distribution of the finite ideal Bose gas. In this expression Nj is directly proportional to gj - 1, where gj and Nj are, respectively, the degeneracy and the most probable occupation number in the degenerate level j. This property agrees with what chemical potential can be quantized if there is a non-degenerate level for the finite ideal Bose gas. Finally, using this expression, we defined a micro-partition function M, obtained the statistical expressions of some thermodynamical quantities.