Boundary effects in classical liquid density fluctuations at finite temperature.

Abstract

We investigate thermal effects on density fluctuations in confined classical liquids using phonon quantization. The system is modeled via a massless scalar field between perfectly reflecting parallel planes with Dirichlet, Neumann, and mixed boundary conditions. Exact closed-form expressions are derived for the mean-square mass density, total energy density, and thermodynamic quantities including Helmholtz free energy and entropy densities. Our analysis identifies distinct regimes, namely, a low-temperature quantum regime exhibiting characteristic power-law behavior for each boundary condition, and a high-temperature classical regime where ℏ-independent behavior emerges as expected. A particularly interesting finding shows that while most quantities transition naturally to classical behavior, the mean-square density fluctuation requires explicit consideration of the ℏ→0 limit. The entropy density vanishes at zero temperature, in agreement with the Nernst heat theorem. Numerical analysis confirms our analytical results, particularly the asymptotic temperature behaviors and the intermediate crossover region, in which quantum and classical effects compete. This regime is governed by the energy scale k_{B}T∼ℏu/a, where a is the distance between the planes and u is the sound velocity.