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arXiv:2401.01838 · The Journal of Physical Chemistry Letters

Resolving the Debate between Boltzmann and Gibbs Entropy: Relative Energy Window Eliminates Thermodynamic Inconsistencies and Allows Negative Absolute Temperatures

Ananth Govind Rajan

Published Sep 4, 2024• 6 citations
arXivHTMLPDF

Abstract

Small systems consisting of a few particles are increasingly technologically relevant. In such systems, an intense debate in microcanonical statistical mechanics has been about the correctness of Boltzmann's surface entropy versus Gibbs' volume entropy. Both entropies have shortcomings─while Boltzmann entropy predicts unphysical negative/infinite absolute temperatures for small systems with an unbounded energy spectrum, Gibbs entropy entirely disallows negative absolute temperatures, in disagreement with experiments. We consider a relative energy window, motivated by the Heisenberg energy-time uncertainty principle and eigenstate thermalization in quantum mechanics. The proposed entropy ensures positive, finite temperatures for systems without a maximum limit on their energy and allows negative absolute temperatures in bounded energy spectrum systems, e.g., with population inversion. It also closely matches canonical ensemble predictions for prototypical systems, thus correctly describing the zero-point energy of an isolated quantum harmonic oscillator. Overall, we enable accurate thermodynamic models for isolated systems with few degrees of freedom.

DOI
10.1021/acs.jpclett.4c02400

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Small systems consisting of a few particles are increasingly technologically relevant. In such systems, an intense debate in microcanonical statistical mechanics has been about the correctness of Boltzmann's surface entropy versus Gibbs' volume entropy. Both entropies have shortcomings─while Boltzmann entropy predicts unphysical negative/infinite absolute temperatures for small systems with an unbounded energy spectrum, Gibbs entropy entirely disallows negative absolute temperatures, in disagreement with experiments. We consider a relative energy window, motivated by the Heisenberg energy-time uncertainty principle and eigenstate thermalization in quantum mechanics. The proposed entropy ensures positive, finite temperatures for systems without a maximum limit on their energy and allows negative absolute temperatures in bounded energy spectrum systems, e.g., with population inversion. It also closely matches canonical ensemble predictions for prototypical systems, thus correctly describing the zero-point energy of an isolated quantum harmonic oscillator. Overall, we enable accurate thermodynamic models for isolated systems with few degrees of freedom.
The proper definition of entropy is fundamental to the relationship between statistical mechanics and thermodynamics. It also plays a major role in the recent debate about the validity of the concept of negative temperature. In this paper, I analyze and calculate the thermodynamic entropy for large but finite quantum mechanical systems. A special feature of this analysis is that the thermodynamic energy of a quantum system is shown to be a continuous variable, rather than being associated with discrete energy eigenvalues. Calculations of the entropy as a function of energy can be carried out with a Legendre transform of thermodynamic potentials obtained from a canonical ensemble. The resultant expressions for the entropy are able to describe equilibrium between quantum systems having incommensurate energy-level spacings. This definition of entropy preserves all required thermodynamic properties, including satisfaction of all postulates and laws of thermodynamics. It demonstrates the consistency of the concept of negative temperature with the principles of thermodynamics.
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The infinite-volume limit of thermodynamic functions calculated in the quantum microcanonical ensemble is shown to exist for a fairly wide class of spin systems and quantum gases. The entropy is set equal to the logarithm of the number of eigenstates in an energy interval which increases linearly with the size of the system, but is otherwise arbitrary. The limiting entropy per unit volume agrees with that calculated in the canonical formalism, and possesses certain convexity properties required for thermodynamic stability. A precise criterion, in terms of the energy spectra of large systems, is given for determining the limit of the thermodynamic entropy as the temperature approaches zero. This is not determined by the degeneracy of the ground state, contrary to the discussion of the ``third law of thermodynamics'' found in some textbooks.
The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples.
In the statistical mechanics of quantum harmonic oscillators, the zero-point energy can either be included (Schrödinger oscillators) or omitted (Planck oscillators). For the usual results, the type of oscillator makes no difference but, looking more closely, it turns out that including or not this energy is not without consequences. The chemical potential μs of a Schrödinger oscillator set is calculated in the canonical formalism and this shows there is a temperature T0 for which μs=0; below this temperature, μs>0. When Planck oscillators are used instead, the chemical potential μp is negative for all temperatures. If the problem is approached in phonon terms and the system is considered to be in contact with a reservoir of particles (conditions of the grand canonical ensemble), a sort of critical temperature Tc is found, for which the number of particles in the system diverges. For Schrödinger oscillators with μs=0, it turns out that Tc=T0, i.e. T0 is a reminder, in the canonical ensemble, of the divergent behavior in the number of particles when under the conditions of the grand canonical ensemble. Also, a modified Einstein solid (MES) model is introduced. In this model the frequency of the oscillators changes with the volume of the solid, and this change is characterized by a certain value of the Grüneisen parameter. The bulk modulus of this solid can be calculated using Planck oscillators, and it becomes negative for certain temperature and volume values, which is physically incorrect. When Schrödinger oscillators are used, the bulk modulus is always positive. Therefore, the different behavior of both types of oscillators would indicate that only Schrödinger oscillators lead to correct results.
We investigate how the temperature calculated from the microcanonical entropy compares with the canonical temperature for finite isolated quantum systems. We concentrate on systems with sizes that make them accessible to numerical exact diagonalization. We thus characterize the deviations from ensemble equivalence at finite sizes. We describe multiple ways to compute the microcanonical entropy and present numerical results for the entropy and temperature computed in these various ways. We show that using an energy window whose width has a particular energy dependence results in a temperature with minimal deviations from the canonical temperature.