SearcharxivSearch

arXiv · 2110.02746

Geometrothermodynamics of van der Waals systems

Abstract

We explore the properties of the equilibrium space of van der Waals thermodynamic systems. We use an invariant representation of the fundamental equation by using the law of corresponding states, which allows us to perform a general analysis for all possible van der Waals systems. The investigation of the equilibrium space is performed by using the Legendre invariant formalism of geometrothermodynamics, which guarantees the independence of the results from the choice of thermodynamic potential. We find all the curvature singularities of the equilibrium space that correspond to first and second order phase transitions. We compare our results with those obtained by using Hessian metrics for the equilibrium space. We conclude that the formalism of geometrothermodynamics allows us to determine the complete phase transition structure of systems with two thermodynamic degrees of freedom.

Explore related subjects

Keep this discovery

BibTeXRIS

Hernando Quevedo, Maria N. Quevedo, Alberto Sanchez. 2021-10-04. Geometrothermodynamics of van der Waals systems. https://doi.org/10.1016/j.geomphys.2022.104495

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