Abstract. Predictions from Hartree-Fock (HF), Popov (P), Yukalov-Yukalova (YY) and t-matrix approximations regarding the thermodynamics from the normal to the BEC phase in weakly interacting Bose gases are considered. By analyzing the dependence of the chemical potential µ on 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 a non-singled valued behavior in the vicinity of the BEC transition, a feature forbidden by general thermodynamic principles. This behavior 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.
A reformulation and generalization of the Zwanzig model (ZW model) for ideal homopolymer chains poly-X, where X represents any of the twenty naturally occurring proteinogenic amino acid residues is presented. This reformulation and generalization provides a direct connection between coarse-grained parameters originally proposed in the ZW model with variables from the Lifson-Roig (LR) theory, such as the helical propensity per residue ω, and new variables introduced here, such as the energy gap Δ between unfolded and folded structures, as well as the ratio f of the energy scales involved. This enables us to discover the relevance of the energy spectrum E to the onset of configurational phase transitions. From the configurational partition function Q, thermodynamic properties such as the configurational entropy S, specific heat v and average energy are calculated in terms of the number of residues K, temperature T, helical propensity ω and energy barrier ΔH for different poly-X chains in vacuo. Results obtained here provide substantial evidence that configurational phase transitions for ideal poly-X chains correspond to first-order phase transitions. An anomalous behavior of the thermodynamic functions , Cv, S with respect to the number K of residues is also highlighted. On-going methods of solution are outlined.
In this work, we address the concept of the chemical potential μ in classical and quantum gases towards the calculation of the equation of state μ = μ(n, T) where n is the particle density and T the absolute temperature using the methods of equilibrium statistical mechanics. Two cases seldom discussed in elementary textbooks are presented with detailed calculations. The first one refers to the explicit calculation of μ for the interacting classical gas exemplified by van der Waals gas. For this purpose, we used the method described by van Kampen (1961 Physica 27 783). The second one refers to the calculation of μ for ideal quantum gases that obey a generalized Pauli's exclusion principle that leads to statistics that go beyond the Bose-Einstein and Fermi-Dirac cases. The audience targeted in this work corresponds mainly to advanced undergraduates and graduate students in the physical-chemical sciences but it is not restricted to them. In regard of this, we have put a special emphasis on showing some additional details of calculations that usually do not appear explicitly in textbooks.
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