https://doi.org/10.1140/epjb/s10051-025-01097-9
Research - Statistical and Nonlinear Physics
Particle-number fluctuations and interspecies correlations in reactive quantum gas mixtures: a reformulation of chemical equilibrium in the canonical ensemble
Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Av. Julian Claveria 8, 33006, Oviedo, Spain
a diogojlrodrigues@gmail.com, uo302765@uniovi.es
Received:
29
July
2025
Accepted:
17
November
2025
Published online:
28
November
2025
The canonical-ensemble description of homogeneous reactive quantum gas mixtures is reformulated by incorporating a single global particle-number conservation constraint over the combined spectra of interconverting species. This constraint replaces the conventional equality of chemical potentials. Fermi–Dirac or Bose–Einstein correlations naturally emerge across one-particle energy eigenstates of species sharing identical spin statistics, which in ergodic single systems manifest as intrinsic features of the equilibrium state. By embedding all microstates linked by conversion pathways, the framework incorporates concentration fluctuations in the statistical description. The formalism offers fresh insights into quantum chemical equilibrium in reactive mixtures with composition fluctuations and smoothly reduces to the classical ideal gas limit via an extended partition function that generalizes classical chemical-equilibrium treatments.
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© The Author(s), under exclusive licence to EDP Sciences, SIF and Springer-Verlag GmbH Germany, part of Springer Nature 2025
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
