Abstract

The onset of quantum behavior in gases is traditionally established through a criterion that is external to classical statistical mechanics. One introduces the thermal de Broglie wavelength and compares it with the mean intermolecular separation, concluding that quantum effects become relevant when nλT3∼1. This condition originates in quantum statistical mechanics and is absent from the classical ideal-gas or van der Waals partition functions. In this work, we show that a grand-canonical treatment of the van der Waals fluid naturally generates an interaction-corrected crossover temperature T3(a,b,m,n) determined by the particle mass, density, and van der Waals interaction parameters. While the thermal de Broglie wavelength provides the standard quantum crossover scale, the interaction-induced correction leading to T3 is obtained without invoking the explicit form of the Bose–Einstein or Fermi–Dirac distributions. Instead, T3 follows from a self-consistent condition within the grand-canonical van der Waals description. We demonstrate that, below this temperature, the statistical assumptions underlying the classical theory become self-inconsistent, indicating the breakdown of the classical description and the onset of the quantum-degenerate regime. The resulting temperature scale therefore provides an interaction-corrected boundary of validity of the classical van der Waals description. These findings provide a new perspective on how intermolecular interactions modify the crossover to the quantum-degenerate regime and clarify the limits of applicability of the classical van der Waals theory.

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