📝 SummarXiv

Abstract

The statistical-mechanical study of the equilibrium properties of fluids, starting from the knowledge of the interparticle interaction potential, is essential to understand the role that microscopic interaction between individual particles play in the properties of the fluid. The study of these properties from a fundamental point of view is therefore a central goal in condensed matter physics. These properties, however, might vary greatly when a fluid is confined to extremely narrow channels and, therefore, must be examined separately. This thesis investigates fluids in narrow pores, where particles are forced to stay in single-file formation and cannot pass one another. The resulting systems are highly anisotropic: motion is free along the channel axis but strongly restricted transversely. To quantify these effects, equilibrium properties of the confined fluids are compared with their bulk counterparts, exposing the role of dimensionality. We also develop a novel theoretical framework based on a mapping approach that converts single-file fluids with nearest-neighbor interactions into an equivalent one-dimensional mixture. This exact isomorphism delivers closed expressions for thermodynamic and structural quantities. It allows us to compute the anisotropic pressure tensor and revises definitions of spatial correlations to take into account spatial anisotropy. The theory is applied to hard-core, square-well, square-shoulder, and anisotropic hard-body models, revealing phenomena such as zigzag ordering and structural crossovers of spatial correlations. Analytical predictions are extensively validated against Monte Carlo and molecular dynamic simulations (both original and from the literature), showing excellent agreement across the studied parameter ranges.