Adsorption of Self-Assembled Rigid Rods on Two-Dimensional Lattices

TL;DR

This study uses Monte Carlo simulations to analyze how self-assembled rigid rods adsorb on 2D lattices, revealing three temperature-dependent regimes and linking adsorption behavior to phase transitions.

Contribution

It provides a detailed characterization of adsorption regimes and phase diagrams for self-assembled rods on square and triangular lattices, combining simulations with analytical predictions.

Findings

Identification of three temperature regimes affecting adsorption behavior.

Adsorption isotherms are sensitive to isotropic-nematic phase transition.

Accurate phase diagrams for square and triangular lattices obtained.

Abstract

Monte Carlo (MC) simulations have been carried out to study the adsorption on square and triangular lattices of particles with two bonding sites that, by decreasing temperature or increasing density, polymerize reversibly into chains with a discrete number of allowed directions and, at the same time, undergo a continuous isotropic-nematic (IN) transition. The process has been monitored by following the behavior of the adsorption isotherms for different values of lateral interaction energy/temperature. The numerical data were compared with mean-field analytical predictions and exact functions for noninteracting and 1D systems. The obtained results revealed the existence of three adsorption regimes in temperature. (1) At high temperatures, above the critical one characterizing the IN transition at full coverage Tc(\theta=1), the particles are distributed at random on the surface and the adlayer behaves as a noninteracting 2D system. (2) At very low temperatures, the asymmetric monomers adsorb forming chains over almost the entire range of coverage, and the adsorption process behaves as a 1D problem. (3) In the intermediate regime, the system exhibits a mixed regime and the filling of the lattice proceeds according to two different processes. In the first stage, the monomers adsorb isotropically on the lattice until the IN transition occurs in the system and, from this point, particles adsorb forming chains so that the adlayer behaves as a 1D fluid. The two adsorption processes are present in the adsorption isotherms, and a marked singularity can be observed that separates both regimes. Thus, the adsorption isotherms appear as sensitive quantities with respect to the IN phase transition, allowing us (i) to reproduce the phase diagram of the system for square lattices and (ii) to obtain an accurate determination of the phase diagram for triangular lattices.