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American Journal of Physics

Equilibrium properties of a mixture of reacting gases: A soluble model

H. J. Kreuzer

Published Oct 1, 1976• 0 citations
Publisher

Abstract

We calculate exactly the equilibrium properties of a large system consisting of two kinds of Bose particles, a and b, that can be transformed into each other by an external field. The enhancement in the specific heat around the threshold (internal excitation) energy of the b particles is studied as a function of the external field strength, and the mass–action law is derived. Bose–Einstein condensation can occur in our mixture of reacting gases at a transition temperature lower than that of a one-component ideal gas. Also, the condensate occupancy increases faster than T3/2 as the temperature is lowered.

DOI
10.1119/1.10242

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We calculate exactly the equilibrium properties of a large system consisting of two kinds of Bose particles, a and b, that can be transformed into each other by an external field. The enhancement in the specific heat around the threshold (internal excitation) energy of the b particles is studied as a function of the external field strength, and the mass–action law is derived. Bose–Einstein condensation can occur in our mixture of reacting gases at a transition temperature lower than that of a one-component ideal gas. Also, the condensate occupancy increases faster than T3/2 as the temperature is lowered.
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.
In experiments on excitons and spin-polarized atomic hydrogen, one deals with a gas involving two Bose branches (for example, paraexcitons and orthoexcitons). Based on a simple model for the coupling between these two components, we discuss how interconversion processes affect Bose condensation in such a system. Our analysis is based on an exact transformation to renormalized Bose particles which are uncoupled. We give results for the condensate fraction as a function of the temperature in the case when the two original Bose particles (a and b) are not in chemical equilibrium (i.e., the chemical potentials ${\mathrm{\ensuremath{\mu}}}_{\mathit{a}}$ and ${\mathrm{\ensuremath{\mu}}}_{\mathit{b}}$ are not equal) as well as in the case of chemical equilibrium (${\mathrm{\ensuremath{\mu}}}_{\mathit{a}}$=${\mathrm{\ensuremath{\mu}}}_{\mathit{b}}$). Our results are of interest in connection with current attempts to observe Bose condensation in atomiclike gases.
Quantum systems consisting of many particles are both interesting from the physics and the mathematics perspective. One aspect that makes them fascinating from the physics point of view is that they can exhibit quantum effects on macroscopic scales such as Bose-Einstein condensation. This phenomenon, first predicted 100 years ago by Bose [19] and Einstein [44], occurs when a dilute gas of bosons is cooled down to very low temperatures. Below a certain critical temperature a condensate forms, meaning that a macroscopic fraction of the particles is in the same one-particle state, and thus, quantum phenomena become relevant on length scales much larger than the individual atom. The occurrence of Bose-Einstein condensation is also related to superfluidity as suggested in [88]. Bose-Einstein condensation has been achieved experimentally independently by the groups of Cornell and Wieman [3] and Ketterle [40] earning them a Nobel prize in 2001. While Bose and Einstein analyzed theoretically the non-interacting gas, an effective theory describing weakly interacting Bose gases was proposed by Bogoliubov in 1947 with the goal of explaining the occurrence of superfluidity in liquid helium [18]. Using assumptions such as that condensation indeed occurs, his theory yields predictions for the low-energy states of the system. Seen from the mathematics perspective, describing the Bose gas is an interesting challenge due to the strong correlations between particles introduced by the interaction making this case much harder to study than the non-interacting one. In particular, a proof that Bose-Einstein condensation occurs in the thermodynamic limit for continuous systems is still out of reach. However, there has been a lot of work regarding the rigorous analysis of bosonic systems in various relevant regimes. This thesis contains three new contributions establishing rigorous results on bosonic systems in different, physically relevant settings. It is based on the articles [37, 27, 31]. The first result concerns the time-evolution of initially trapped Bose gases in the ultra-dilute Gross-Pitaevskii regime. Under some assumptions on the initial data satisfied in particular by a class of states that are expected to approximate the ground state in a trap, we derive a quasi-free approximation that is close to the true solution in L2L^2L2-norm. In particular, we show that this approximate wave function is described in terms of a Bose-Einstein condensate in a one-particle state following the time-dependent Gross-Pitaevskii equation together with pair excitations with respect to this condensate. As a corollary, we establish a central limit theorem for bounded one-particle observables. The second result is a simple proof of Bose-Einstein condensation for interacting, ultra-dilute gases. More specifically, we consider scalings interpolating between the Gross-Pitaevskii regime and the thermodynamic limit. While condensation had been shown to hold in these regimes before, the advantage of the method used here is its simplicity. Lastly, the third result establishes an upper bound on the ground state energy of a dilute Bose gas in the thermodynamic limit. It captures rigorously the third order correction to the energy per unit volume for sufficiently low densities as predicted in the physics literature first by Wu and subsequently others. Full-text embargoed until: 2026-01-01\textit{Full-text embargoed until: 2026-01-01}Full-text embargoed until: 2026-01-01
The thermodynamic properties of a Bose gas of particles with nonzero spin and magnetic moment in states with and without a Bose-Einstein condensate are studied as a function of the external magnetic field. It is shown that there exists a temperature interval where a transition into a state with a Bose-Einstein condensate occurs in a Bose gas with constant temperature and particle number density when the magnetic field is increasing and reaches a critical magnitude. The temperature and magnetic field derivatives of the specific heat at constant volume and the magnetic susceptibility undergo a jump at such a transition.
We study the thermodynamic properties of binary Bose mixtures by developing a beyond mean-field Popov theory which properly includes the effects of quantum and thermal fluctuations in both the density and spin channels. Results for key thermodynamic quantities, such as the isothermal compressibility and the magnetic susceptibility, are derived from a perturbative calculation of the grand-canonical potential. We find that thermal fluctuations can play a crucial role on the miscibility condition of a binary mixture, favoring phase separation at finite temperature even if the mixture is soluble at zero temperature, as already anticipated in a previous work [M. Ota et al., Phys. Rev. Lett. 123, 075301 (2019)]. We further investigate the miscibility condition for binary mixtures in the presence of asymmetry in the intraspecies interactions, as well as in the masses of the two components. Furthermore, we discuss the superfluid behavior of the mixture and the temperature dependence of the Andreev-Bashkin effect.