F. Romá

Configurational entropy for adsorbed linear species (k-mers)

The configurational entropy of interacting linear molecules (k-mers) absorbed on a regular lattice is addressed through analytical as well as numerical methods. The general definitions for computational exact calculations of k-mers lattice-gas entropy are presented. In addition, theoretical basis for accurate analytical estimations of the entropy of reference states are given. The coverage and temperature dependence of the configurational entropy of interacting adsorbed dimers on one and two-dimensional lattices are obtained. A novel phase behavior of k-mers lattice-gas is shown and discussed.

Surface area measurements with linear adsorbates: an experimental comparison of different theoretical approaches.

The specific area of a substrate was determined from the results of adsorption isotherms performed with a sequence of four alkanes, from methane to butane, using three different approaches. The data were first analyzed using the BET equation and the point B methods; these results were compared with those obtained using a new equation designed for examining the case of multisite occupancy. The new model specifically accounts for sites that are left uncovered in the case of adsorption by linear adsorbates. Of these three, only the last method gives essentially the same value for the specific surface area of the substrate when different adsorbates are used to measure it. The other two, more traditional, approaches give values of the specific surface area that decrease as the length of the adsorbate used increases.

First-order phase transitions in repulsive rigid k-mers on two-dimensional lattices.

In a previous paper [F. Romá, A. J. Ramirez-Pastor, and J. L. Riccardo, Phys. Rev. B 72, 035444 (2005)], the critical behavior of repulsive rigid rods of length k (k-mers) on a square lattice at half coverage has been studied by using Monte Carlo (MC) simulations. The obtained results indicated that (1) the phase transition occurring in the system is a second-order phase transition for all adsorbate sizes k; and (2) the universality class of the transition changes from 2D Ising-type for monomers (k = 1) to an unknown universality class for k ≥ 2. In the present work, we revisit our previous results together with further numerical evidences, resulting from new extensive MC simulations based on an efficient exchange algorithm and using high-performance computational capabilities. In contrast to our previous conclusions (1) and (2), the new numerical calculations clearly support the occurrence of a first-order phase transition for k ≥ 2. In addition, a similar scenario was found for k-mers adsorbed on the triangular lattice at coverage k/(2k+1).

Statistical Thermodynamics and Surface Phase Transitions of Interacting Particles Adsorbed on One-Dimensional Channels Arranged in a Triangular Cross-Sectional Structure

Monte Carlo simulations and finite-size scaling analysis have been carried out to study the critical behavior in a submonolayer lattice-gas, which mimics a nanoporous environment. In this model, one-dimensional chains of atoms were arranged in a triangular cross-sectional structure. Two kinds of lateral interaction energies have been considered: (1) wL, interaction energy between nearest-neighbor particles adsorbed along a single channel and (2) wT, interaction energy between particles adsorbed across nearest-neighbor channels. We focus on the case of repulsive transverse interactions (wT > 0), where a rich variety of structural orderings are observed in the adlayer, depending on the value of the parameters kBT/wT (kB being the Boltzmann constant) and wL /wT. For wL /wT = 0, successive planes are uncorrelated, the system is equivalent to the triangular lattice, and the well-known [ ] ordered phase is found at low temperatures and a coverage, , of 1/3 [2/3]. In the more general case (wL /wT  0), the competition between interactions along a single channel and the transverse coupling between sites in neighboring channels leads to a three-dimensional adsorbed layer. Consequently, the and structures “propagate” along the channels and new ordered phases appear in the adlayer. The influence of each ordered phase on adsorption isotherms, differential heat of adsorption and configurational entropy of the adlayer has been analyzed and discussed in the context of the lattice-gas theory. Finally, the Monte Carlo technique was combined with the recently reported free energy minimization criterion approach (FEMCA) [F. Romá et al.: Phys. Rev. B Vol. 68 (2003), art. no. 205407] to predict the critical temperatures of the surface-phase transformations occurring in the adsorbate. The excellent qualitative agreement between simulated data and FEMCA results allows us to interpret the physical meaning of the mechanisms underlying the observed transitions.

Adsorption and transport of polyatomic species in one-dimensional systems: exact forms of the thermodynamic functions and chemical diffusion coefficient

Abstract The thermodynamic functions of k-mers adsorbed in a simple model of quasi-one-dimensional nanotubess adsorption potential are exactly evaluated. The adsorption sites are assumed to lie in a regular one-dimensional space, and calculations are carried out in the lattice-gas approximation. The coverage and temperature dependance of the free energy, chemical potential and entropy are given. The collective relaxation of density fluctuations is addressed; the dependence of chemical diffusion coefficient on coverage and adsorbate size is calculated rigorously and related to features of the configurational entropy.