Rigid Rods Of Length Research Articles

Entropy-driven phases at high coverage adsorption of straight rigid rods on two-dimensional square lattices.

Polymers are frequently deposited on different surfaces, which has attracted the attention of scientists from different viewpoints. In the present approach polymers are represented by rigid rods of length k (k-mers), and the substrate takes the form of an L×L square lattice whose lattice constant matches exactly the interspacing between consecutive elements of the k-mer chain. We briefly review the classical description of the nematic transition presented by this system for k≥7 observing that the high-coverage (θ) transition deserves a more careful analysis from the entropy point of view. We present a possible viewpoint for this analysis that justifies the phase transitions. Moreover, we perform Monte Carlo (MC) simulations in the grand canonical ensemble, supplemented by thermodynamic integration, to first calculate the configurational entropy of the adsorbed phase as a function of the coverage, and then to explore the different phases (and orientational transitions) that appear on the surface with increasing the density of adsorbed k-mers. In the limit of θ→1 (full coverage) the configurational entropy is obtained for values of k ranging between 2 and 10. MC data are discussed in comparison with recent analytical results [D. Dhar and R. Rajesh, Phys. Rev. E 103, 042130 (2021)2470-004510.1103/PhysRevE.103.042130]. The comparative study allows us to establish the applicability range of the theoretical predictions. Finally, the structure of the high-coverage phase is characterized in terms of the statistics of k×l domains (domains of l parallel k-mers adsorbed on the surface). A distribution of finite values of l (l≪L) is found with a predominance of k×1 (single k-mers) and k×k domains. The distribution is the same in each lattice direction, confirming that at high density the adsorbed phase goes to a state with mixed orientations and no orientational preference. An order parameter measuring the number of k×k domains in the adsorbed layer is introduced.

Elastic response of wire frame glasses. I. Two dimensional model.

We study the elastic response of concentrated suspensions of rigid wire frame particles to a step strain. These particles are constructed from infinitely thin, rigid rods of length L. We specifically compare straight rod-like particles to bent and branched wire frames. In dense suspensions, the wire frames are frozen in a disordered state by the topological entanglements between their arms. We present a simple, geometric method to find the scaling of the elastic stress with concentration in these glassy systems. We apply this method to a simple 2D model system where a test particle is placed on a plane and constrained by a random distribution of points with number density ν. Two striking differences between wire frame and rod suspensions are found: (1) The linear elasticity per particle for wire frames is very large, scaling like ν2L4, whereas for rods, it is much smaller and independent of concentration. (2) Rods always shear thin but wire frames shear harden for concentrations less than ∼K/kBTL4, where K is the bending modulus of the particles. The deformation of wire frames is found to be important even for small strains, with the proportion of deformed particles at a particular strain, γ, being given by (νL2)2γ2. Our results agree well with simple numerical calculations for the 2D system.

Nematic-disordered phase transition in systems of long rigid rods on two-dimensional lattices

We study the phase transition from a nematic phase to a high-density disordered phase in systems of long rigid rods of length $k$ on the square and triangular lattices. We use an efficient Monte Carlo scheme that partly overcomes the problem of very large relaxation times of nearly jammed configurations. The existence of a continuous transition is observed on both lattices for $k=7$. We study correlations in the high-density disordered phase, and we find evidence of a crossover length scale $\xi^* \gtrsim 1400$, on the square lattice. For distances smaller than $\xi^*$, correlations appear to decay algebraically. Our best estimates of the critical exponents differ from those of the Ising model, but we cannot rule out a crossover to Ising universality class at length scales $\gg \xi^*$. On the triangular lattice, the critical exponents are consistent with those of the two dimensional three-state Potts universality class.

Statistical thermodynamics of straight rigid rods with nonadditive lateral interactions: Theory and Monte Carlo simulations

The statistical thermodynamics of straight rigid rods of length k (k-mers) with nonadditive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical Bragg-Williams approximation (BWA) and the quasichemical approximation (QCA). The new theoretical framework is obtained by combining (i) the exact analytical expression for the partition function of noninteracting linear k-mers adsorbed in one dimension and its extension to higher dimensions, and (ii) a generalization of BWA and QCA in which the adsorbate can occupy more than one adsorption site. The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The coverage and temperature dependence of the Helmholtz free energy, chemical potential, configurational entropy, and differential heat of adsorption are given. The formalism (i) reproduces the classical results for monomers, (ii) leads to the exact statistical thermodynamics of nonadditive interacting k-mers adsorbed in one dimension, and (iii) provides a close approximation for two-dimensional systems, taking into account multisite occupancy and nonadditive lateral interactions. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model. Significant quantitative differences are shown and discussed. In all cases, the QCA appears to be the more accurate approach.

Self-consistent-field approximation for a one-dimensional many-body system: Fermions

The self-consistent-field approximation is applied for the study of the energy spectrum, sound velocity, and correlation function on a one-dimensional, spin-1/2 Fermi system, interacting as rigid rods of length $l$. Two very distinct regions are observed, which are named as low- and high-density behaviors, corresponding to small and large Landau's ${F}_{0}$, respectively. The results are very similar to those obtained for a boson system with the same type of interaction, as one might expect. For the very high densities the energy spectrum approaches the $E(q)=0$ line, indicating the existence of an instability, a liquid to crystal transition, which is very neatly followed by observing the behavior of the pair-correlation function as density increases.