SearcharxivSearch

arXiv · 2305.13513

On the relation between thermodynamical and statistical entropy: The origin of the N!

Abstract

The division by N! in the expression of statistical entropy is usually justified to students by the statement that classical particles should be counted as indistinguishable. Sometimes, quantum indistinguishability is invoked to explain it. In this paper, we try to clarify the issue starting from Clausius thermodynamical entropy and deriving from it Boltzmann statistical entropy for the ideal gas. This approach appears interesting for two reasons: Firstly, it provides a direct heuristic link between thermodynamical and statistical expressions of entropy that is missing in the usual approach. In second place, it explicitly reminds that also statistical entropy is defined with respect to a reference state, chosen to be the quantum-mechanical (T=0) ground state of the N-particles in a box. Both factors $h^{3N}$ and $N!$ at the denominator of the statistical entropy are a consequence of the quantum nature of the reference state: in particular, the $N!$ is not related to the particle identity, but to the identity of the boundary conditions on the quantum-mechanical ground-state momenta, and to a general statistical maximization principle. The introduction of a reference state also allows to reinterpret the standard case of two mixing gases.

Explore related subjects

Keep this discovery

BibTeXRIS

Sergio Di Matteo. 2023-05-22. On the relation between thermodynamical and statistical entropy: The origin of the N!. https://arxiv.org/abs/2305.13513

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Universal sampling of spin systems across quenched disorder

Statistical physics extracts macroscopic laws by averaging over the many microscopic degrees of freedom of a system. Disordered systems demand a second and far harder average, one over the quenched randomness itself. The classic analytical routes, the replica and cavity methods, become uncontrolled outside mean-field or tree-like limits, and conventional numerical algorithms like parallel tempering require expensive, independent equilibration for every disorder realization. In this work, we introduce a universal neural variational framework that amortizes inference across the disorder ensemble, eliminating both the need for per-instance Markov chain equilibration and the cost of retraining instance-specific variational ansatzes. Built on an encoder-decoder Transformer architecture, after training once, it produces an explicit approximation to the Boltzmann distribution given previously unseen disorder realizations without further optimization. We validate this framework on 2D Edwards-Anderson models, and apply it to the random-bond Ising model, successfully capturing the Binder cumulant crossings near the Nishimori multicritical point. These results shift the object of variational inference from the single instance to the disorder ensemble, opening a route to frustrated many-body systems where instance-by-instance computation is prohibitive.

cond-mat.stat-mech

Information-Theoretic Characterization of Macroscopic Chaos Emerging from the Chemical Master Equation

Open chemical reaction networks exhibit stochastic concentration dynamics at finite system sizes, whereas their macroscopic limit is governed by deterministic rate equations that can display chaos. In this Letter, we show theoretically that a rate of information loss constructed from two-time mutual information recovers the Kolmogorov-Sinai entropy in the deterministic limit. We verify this result through numerical simulations of a Markov jump process for a three-species system involving seven reactions.

cond-mat.stat-mech

Orientational order on non-orientable domains

We study the statistical properties of passive and active many-body systems with orientational degrees of freedom on non-orientable domains. By rephrasing topological constraints as non-local symmetry relations on an orientable double-cover, we show that non-orientability eliminates global rotational soft modes without acting like an external field. In a passive XY model, this results in topological caging, where orientational fluctuations that exhibit conventional diffusive behavior on a torus saturate on a Klein bottle to a finite value that we compute exactly in the thermodynamic limit. In models of active self-propelled particles with orientational degrees of freedom, topological caging persists despite continuously changing interaction neighborhoods. In an active Ising spin model, non-orientability enforces the coexistence of ordered anti-parallel domains with vanishing global polar order, a state that is absent on orientable domains.

cond-mat.stat-mech