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

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.Comment: Langmuir, 201

Adsorption preference reversal phenomenon from multisite-occupancy theory fortwo-dimensional lattices

The statistical thermodynamics of polyatomic species mixtures adsorbed on two-dimensional substrates was developed on a generalization in the spirit of the lattice-gas model and the classical Guggenheim-DiMarzio approximation. In this scheme, the coverage and temperature dependence of the Helmholtz free energy and chemical potential are given. The formalism leads to the exact statistical thermodynamics of binary mixtures adsorbed in one dimension, provides a close approximation for two-dimensional systems accounting multisite occupancy and allows to discuss the dimensionality and lattice structure effects on the known phenomenon of adsorption preference reversal.Comment: 13 pages, 4 figure

The effect of the lateral interactions on the critical behavior of long straight rigid rods on two-dimensional lattices

Using Monte Carlo simulations and finite-size scaling analysis, the critical behavior of attractive rigid rods of length k (k-mers) on square lattices at intermediate density has been studied. A nematic phase, characterized by a big domain of parallel k-mers, was found. This ordered phase is separated from the isotropic state by a continuous transition occurring at a intermediate density \theta_c, which increases linearly with the magnitude of the lateral interactions.Comment: 7 pages, 6 figure

Entropy-driven phase transition in a system of long rods on a square lattice

The isotropic-nematic (I-N) phase transition in a system of long straight rigid rods of length k on square lattices is studied by combining Monte Carlo simulations and theoretical analysis. The process is analyzed by comparing the configurational entropy of the system with the corresponding to a fully aligned system, whose calculation reduces to the 1D case. The results obtained (1) allow to estimate the minimum value of k which leads to the formation of a nematic phase and provide an interesting interpretation of this critical value; (2) provide numerical evidence on the existence of a second phase transition (from a nematic to a non-nematic state) occurring at density close to 1 and (3) allow to test the predictions of the main theoretical models developed to treat the polymers adsorption problem.Comment: 14 pages, 6 figures. Accepted for publication in JSTA

Critical behavior of self-assembled rigid rods on triangular and honeycomb lattices

Using Monte Carlo simulations and finite-size scaling analysis, the critical behavior of self-assembled rigid rods on triangular and honeycomb lattices at intermediate density has been studied. The system is composed of monomers with two attractive (sticky) poles that, by decreasing temperature or increasing density, polymerize reversibly into chains with three allowed directions and, at the same time, undergo a continuous isotropic-nematic (IN) transition. The determination of the critical exponents, along with the behavior of Binder cumulants, indicate that the IN transition belongs to the q=1 Potts universality class.Comment: 6 pages, 5 figure

Critical behavior of long straight rigid rods on two-dimensional lattices: Theory and Monte Carlo simulations

The critical behavior of long straight rigid rods of length $k$ ($k$-mers) on square and triangular lattices at intermediate density has been studied. A nematic phase, characterized by a big domain of parallel $k$-mers, was found. This ordered phase is separated from the isotropic state by a continuous transition occurring at a intermediate density $\theta_c$. Two analytical techniques were combined with Monte Carlo simulations to predict the dependence of $\theta_c$ on $k$, being $\theta_c(k) \propto k^{-1}$. The first involves simple geometrical arguments, while the second is based on entropy considerations. Our analysis allowed us also to determine the minimum value of $k$ ($k_{min}=7$), which allows the formation of a nematic phase on a triangular lattice.Comment: 23 pages, 5 figures, to appear in The Journal of Chemical Physic