Statistical Mechanics of Linear k-mer Lattice Gases: From Theory to Applications

The statistical mechanics of structured particles with arbitrary size and shape adsorbed onto discrete lattices presents a longstanding theoretical challenge, mainly due to complex spatial correlations and entropic effects that emerge at finite densities. Even for simplified systems such as hard-core linear k-mers, exact solutions remain limited to low-dimensional or highly constrained cases. In this review, we summarize the main theoretical approaches developed by our research group over the past three decades to describe adsorption phenomena involving linear k-mers—also known as multisite occupancy adsorption—on regular lattices. We examine modern approximations such as an extension to two dimensions of the exact thermodynamic functions obtained in one dimension, the Fractional Statistical Theory of Adsorption based on Haldane’s fractional statistics, and the so-called Occupation Balance based on expansion of the reciprocal of the fugacity, and hybrid approaches such as the semi-empirical model obtained by combining exact one-dimensional calculations and the Guggenheim–DiMarzio approach. For interacting systems, statistical thermodynamics is explored within generalized Bragg–Williams and quasi-chemical frameworks. Particular focus is given to the recently proposed Multiple Exclusion statistics, which capture the correlated exclusion effects inherent to non-monomeric particles. Applications to monolayer and multilayer adsorption are analyzed, with relevance to hydrocarbon separation technologies. Finally, computational strategies, including advanced Monte Carlo techniques, are reviewed in the context of high-density regimes. This work provides a unified framework for understanding entropic and cooperative effects in lattice-adsorbed polyatomic systems and highlights promising directions for future theoretical and computational research.