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arXiv:1903.02121 · The Journal of Chemical Physics

The generalized Boltzmann distribution is the only distribution in which the Gibbs-Shannon entropy equals the thermodynamic entropy

Xiang Gao, Emilio Gallicchio, Adrian E. Roitberg

Published Jul 19, 2019• 37 citations
arXivHTMLPDF

Abstract

We show that the generalized Boltzmann distribution is the only distribution for which the Gibbs-Shannon entropy equals the thermodynamic entropy. This result means that the thermodynamic entropy and the Gibbs-Shannon entropy are not generally equal, but rather the equality holds only in the special case where a system is in equilibrium with a reservoir.

DOI
10.1063/1.5111333

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We show that the generalized Boltzmann distribution is the only distribution for which the Gibbs-Shannon entropy equals the thermodynamic entropy. This result means that the thermodynamic entropy and the Gibbs-Shannon entropy are not generally equal, but rather the equality holds only in the special case where a system is in equilibrium with a reservoir.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
We derive Bose-Einstein statistics and Fermi-Dirac statistics by Principle of Maximum Entropy applied to two families of entropy functions different from the Boltzmann-Gibbs-Shannon entropy. These entropy functions are identified with special cases of modified Naudts' ϕϕϕ-entropy.
We explore the perspective of considering the squeezed thermal reservoir as an equilibrium reservoir in a generalized Gibbs ensemble with two noncommuting conserved quantities. We outline the main properties of such a reservoir in terms of the exchange of energy, both heat and work, and entropy, giving some key examples to clarify its physical interpretation. This allows for a correct and insightful interpretation of all thermodynamical features of the squeezed thermal reservoir, as well as other similar nonthermal reservoirs, including the characterization of reversibility and the first and second laws of thermodynamics.
In this work, we compare three formulations of thermodynamic entropy for a non-interacting bosonic gas: (i) the grand-canonical Bose-Einstein entropy, (ii) the finite-N canonical entropy obtained from the exact partition function (Ziff, Uhlenbeck, and Kac construction), and (iii) the entropy of a multinomial distribution with Boltzmann categorical probabilities and temperature determined from Clausius' equation. It is well-known that the grand-canonical Bose-Einstein systematically overestimates entropy of canonical systems in regimes where particle-number fluctuations are significant. The exact canonical entropy correctly enforces the particle-number constraint, but recent experimental results suggest that it also overestimates particle-number fluctuations below the crossover temperature. The multinomial distribution is less common in thermodynamics. It addresses in a mathematically exact way the puzzle of the famous -log(N!) term introduced by Gibbs as a deus ex machina in discussions of thermodynamic entropy. One remarkable consequence is that the entropy of the multinomial distribution overcomes the issue of negative entropy at low temperature that affects the Gibbs and the Sackur-Tetrode entropies at low temperature. The analysis presented in the paper shows that the multinomial distribution, equipped with a categorical distribution calibrated in such a way that the resulting multinomial entropy fits Clausius' equation, provides accurate approximations to the canonical entropy in the classical regime, while it is smaller than the canonical entropy below the crossover temperature. One feature of the multinomial distribution is that it predicts lower peak variance of the number of particles in the ground state than the canonical distribution. This is in agreement with recent experimental results; hence, this paper identifies the thermodynamically calibrated multinomial distribution as a candidate alternative to the canonical distribution for thermodynamic bosonic entropy in finite systems.