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Statistical thermodynamics of particles having a spectrum of topological correlated states and observing statistical exclusion is developed to describe mixtures of species of arbitrary size and shape. A generalized statistical distribution is obtained through a configuration space ansatz recently introduced for single species accounting for the multiple exclusion statistical phenomena, where spatially correlated particle states can be simultaneously excluded by more than one particle. Statistical exclusion on a correlated states spectrum is characterized by exclusion statistical parameters β_{cij} which are self-consistently determined within the multiple exclusion from thermodynamic boundary conditions. Self-exclusion and cross-exclusion frequency functions e_{ij}(n) and average cumulative exclusion functions G_{ij}(n) are introduced to characterize the state exclusion spectrum as density varies. Haldane's statistics and Wu's distribution for statistically independent excluding species are recovered in the limit of uncorrelated states for single species as well as for mixtures of self- and cross-excluding species with constant mutual statistical exclusion. The multiple exclusion statistics formalism is applied to the k-mer problem on a square lattice rationalized as a mixture of two differently oriented self-excluding and cross-excluding pseudospecies. An isotropic-nematic and a high-density nematic-isotropic (disordered) phase transitions is predicted only for k≥7. The isotropic-nematic transition is continuum as expected, but the high-density transition results in a first-order one. The formalism provides phase coexistence lines and the chemical potential dependence of the low- and high-density branches in the nematic regime. The theoretical approach to lattice gases presented in this work offers a unique general framework applicable to mixtures of entropy-complex lattice gases. From this framework, k-mer phase transitions can be reproduced, and significant configuration features can be derived from the state exclusion spectrum functions.

The thermodynamic properties of sI clathrate hydrates involving methane and carbon dioxide guest molecules have been investigated using Monte Carlo (MC) simulations in the grand canonical ensemble, and analytical cluster approximation (CA) theory. The CA approach is founded on the precise calculation of states within finite cells. Both the sI hydrate structure and the guest species were represented using a two-dimensional triangular lattice-gas model with single- and multiple-site occupancy. The investigation entailed monitoring the lattice coverage's dependence on the chemical potential (adsorption isotherm) and examining quantities like Helmholtz free energy, energy of the adsorbed phase, configurational entropy, and adsorption heat. Three distinct scenarios were considered, each dependent on the intra- and interspecies interactions. First, the study was restricted to an ideal clathrate hydrate, wherein lateral interactions were disregarded, and the system's properties are governed by entropy alone. Second, lateral interactions between the guest species and water molecules were introduced by employing the well-established Lorentz-Berthelot mixing rules. Lastly, repulsive lateral interactions were taken into account. In all cases, a remarkable agreement between the results obtained through CA and MC was observed, underscoring the significant potential of CA theory as a valuable tool for exploring cavity occupancy and selectivity in the sI clathrate hydrate formation process.

Random sequential adsorption of extended objects deposited on two-dimensional regular lattices is studied. The depositing objects are chains formed by occupying adsorption sites on the substrate through a self-avoiding walk of k lattice steps; these objects are also called "tortuous k-mers." We study how the jamming coverage, θ_{j,k}, depends on k for lattices with different connectivity (honeycomb, square, and triangular). The dependence can be fitted by the function θ_{j,k}=θ_{j,k→∞}+B/k+C/k^{2}, where B and C are found to be shared parameters by the three lattices and θ_{j,k→∞} (>0) is the jamming coverage for infinitely long k-mers for each of them. The jamming coverage is found to have a growing behavior with the connectivity of the lattice. In addition, θ_{j,k} is found to be higher for tortuous k-mers than for the previously reported for linear k-mers in each lattice. The results were obtained by means of numerical simulation through an efficient algorithm whose characteristics are discussed in detail. The computational method introduced here also allows us to investigate the full-time kinetics of the surface coverage θ_{k}(t) [θ_{j,k}≡θ_{k}(t→∞)]. Along this line, different time regimes are identified and characterized.

Numerical simulations and finite-size scaling analysis have been carried out to study the problem of inverse percolation by removing semirigid rods from a L×L square lattice that contains two layers (and M=L×L×2 sites). The process starts with an initial configuration where all lattice sites are occupied by single monomers (each monomer occupies one lattice site) and, consequently, the opposite sides of the lattice are connected by nearest-neighbor occupied sites. Then the system is diluted by removing groups of k consecutive monomers according to a generalized random sequential adsorption mechanism. The study is conducted by following the behavior of two critical concentrations with size k: (1) jamming coverage θ_{j,k}, which represents the concentration of occupied sites at which the jamming state is reached, and (2) inverse percolation threshold θ_{c,k}, which corresponds to the maximum concentration of occupied sites for which connectivity disappears. The obtained results indicate that (1) the jamming coverage exhibits an increasing dependence on the size k-it rapidly increases for small values of k and asymptotically converges towards a definite value for infinitely large k sizes θ_{j,k→∞}≈0.2701-and (2) the inverse percolation threshold is a decreasing function of k in the range 1≤k≤17. For k≥18, all jammed configurations are percolating states (the lattice remains connected even when the highest allowed concentration of removed sites is reached) and, consequently, there is no nonpercolating phase. This finding contrasts with the results obtained in literature for a complementary problem, where straight rigid k-mers are randomly and irreversibly deposited on a square lattice forming two layers. In this case, percolating and nonpercolating phases extend to infinity in the space of the parameter k and the model presents percolation transition for the whole range of k. The results obtained in the present study were also compared with those reported for the case of inverse percolation by removal of rigid linear k-mers from a square monolayer. The differences observed between monolayer and bilayer problems were discussed in terms of vulnerability and network robustness. Finally, the accurate determination of the critical exponents ν, β, and γ reveals that the percolation phase transition involved in the system has the same universality class as the standard percolation problem.

Combining Monte Carlo simulations and thermodynamic integration method, we study the configurational entropy per site of straight rigid rods of length k (k-mers) adsorbed on three-dimensional (3D) simple cubic lattices. The process is monitored by following the dependence of the lattice coverage θ on the chemical potential μ (adsorption isotherm). Then, we perform the integration of μ(θ) over θ to calculate the configurational entropy per site of the adsorbed phase s(k,θ) as a function of the coverage. Based on the behavior of the function s(k,θ), different phase diagrams are obtained according to the k values: k≤4, disordered phase; k=5,6, disordered and layered-disordered phases; and k≥7, disordered, nematic and layered-disordered phases. In the limit of θ→1 (full coverage), the configurational entropy per site is determined for values of k ranging between 2 and 8. For k≥6, MC data coincide (within the statistical uncertainty) with recent analytical predictions [D. Dhar and R. Rajesh, Phys. Rev. E 103, 042130 (2021)2470-004510.1103/PhysRevE.103.042130] for very large rods. This finding represents the first numerical validation of the expression obtained by Dhar and Rajesh for d-dimensional lattices with d>2. In addition, for k≥5, the values of s(k,θ→1) for simple cubic lattices are coincident with those values reported in [P. M. Pasinetti et al., Phys. Rev. E 104, 054136 (2021)2470-004510.1103/PhysRevE.104.054136] for two-dimensional (2D) square lattices. This is consistent with the picture that at high densities and k≥5, the layered-disordered phase is formed on the lattice. Under these conditions, the system breaks to 2D layers, and the adsorbed phase becomes essentially 2D. The 2D behavior of the fully covered lattice reinforces the conjecture that the large-k behavior of entropy per site is superuniversal, and holds on d-dimensional hypercubical lattices for all d≥2.

Monte Carlo simulations and finite-size scaling theory have been carried out to study the critical behavior and universality for the isotropic-nematic (IN) phase transition in a system of straight rigid pentamers adsorbed on a triangular lattice with polarized nonhomogeneous intermolecular interactions. The model was inspired by the deposition of 2-thiophene molecules over the Au(111) surface, which was previously characterized by experimental techniques and density functional theory. A nematic phase, observed experimentally by the formation of a self-assembled monolayer of parallel molecules, is separated from the isotropic state by a continuous transition occurring at a finite density. The precise determination of the critical exponents indicates that the transition belongs to the three-state Potts universality class. The finite-size scaling analysis includes the study of mutability and diversity. These two quantities are derived from information theory and they have not previously been considered as part of the conventional treatment of critical phenomena for the determination of critical exponents. The results obtained here contribute to the understanding of formation processes of self-assembled monolayers, phase transitions, and critical phenomena from novel compression algorithms for studying mutual information in sequences of data.

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.

Surface growth properties during irreversible multilayer deposition of straight semirigid rods on linear and square lattices have been studied by Monte Carlo simulations and analytical considerations. The filling of the lattice is carried out following a generalized random sequential adsorption mechanism where the depositing objects can be adsorbed on the surface forming multilayers. The results of our simulations show that the roughness evolves in time following two different behaviors: an "homogeneous growth regime" at initial times, where the heights of the columns homogeneously increase, and a "segmented growth regime" at long times, where the adsorbed phase is segmented in actively growing columns and inactive nongrowing sites. Under these conditions, the surface growth generated by the deposition of particles of different sizes is studied. At long times, the roughness of the systems increases linearly with time, with growth exponent β=1, at variance with a random deposition of monomers which presents a sublinear behavior (β=1/2). The linear behavior is due to the segmented growth process, as we show using a simple analytical model.

Numerical simulations and finite-size scaling analysis have been carried out to study standard and inverse percolation of straight rigid rods on triangular lattices. In the case of standard percolation, the lattice is initially empty. Then, linear k-mers (particles occupying k consecutive sites along one of the lattice directions) are randomly and sequentially deposited on the lattice. In the case of inverse percolation, the process starts with an initial configuration where all lattice sites are occupied by single monomers (each monomer occupies one lattice site) and, consequently, the opposite sides of the lattice are connected by nearest-neighbor occupied sites. Then the system is diluted by randomly removing sets of k consecutive monomers (linear k-mers) from the lattice. Two schemes are used for the depositing/removing process: an isotropic scheme, where the deposition (removal) of the linear objects occurs with the same probability in any lattice direction, and an anisotropic (perfectly oriented) scheme, where one lattice direction is privileged for depositing (removing) the particles. The study is conducted by following the behavior of four critical concentrations with size k: (i) [(ii)] standard isotropic[oriented] percolation threshold θ_{c,k}[ϑ_{c,k}], which represents the minimum concentration of occupied sites at which an infinite cluster of occupied nearest-neighbor sites extends from one side of the system to the other. θ_{c,k}[ϑ_{c,k}] is reached by isotropic[oriented] deposition of straight rigid k-mers on an initially empty lattice; and (iii) [(iv)] inverse isotropic[oriented] percolation threshold θ_{c,k}^{i}[ϑ_{c,k}^{i}], which corresponds to the maximum concentration of occupied sites for which connectivity disappears. θ_{c,k}^{i}[ϑ_{c,k}^{i}] is reached after removing isotropic [completely aligned] straight rigid k-mers from an initially fully occupied lattice. θ_{c,k}, ϑ_{c,k}, θ_{c,k}^{i}, and ϑ_{c,k}^{i} are determined for a wide range of k (2≤k≤512). The obtained results indicate that (1)θ_{c,k}[θ_{c,k}^{i}] exhibits a nonmonotonous dependence on the size k. It decreases[increases] for small particle sizes, goes through a minimum[maximum] at around k=11, and finally increases and asymptotically converges towards a definite value for large segments θ_{c,k→∞}=0.500(2) [θ_{c,k→∞}^{i}=0.500(1)]; (2)ϑ_{c,k}[ϑ_{c,k}^{i}] depicts a monotonous behavior in terms of k. It rapidly increases[decreases] for small particle sizes and asymptotically converges towards a definite value for infinitely long k-mers ϑ_{c,k→∞}=0.5334(6) [ϑ_{c,k→∞}^{i}=0.4666(6)]; (3) for both isotropic and perfectly oriented models, the curves of standard and inverse percolation thresholds are symmetric to each other with respect to the line θ(ϑ)=0.5. Thus a complementary property is found θ_{c,k}+θ_{c,k}^{i}=1 (and ϑ_{c,k}+ϑ_{c,k}^{i}=1) which has not been observed in other regular lattices. This condition is analytically validated by using exact enumeration of configurations for small systems, and (4) in all cases, the critical concentration curves divide the θ space in a percolating region and a nonpercolating region. These phases extend to infinity in the space of the parameter k so that the model presents percolation transition for the whole range of k.

The site-bond percolation problem in two-dimensional kagome lattices has been studied by means of theoretical modeling and numerical simulations. Motivated by considerations of cluster connectivity, two distinct schemes (denoted as S∩B and S∪B) have been considered. In S∩B (S∪B), two points are connected if a sequence of occupied sites and (or) bonds joins them. Analytical and simulation approaches, supplemented by analysis using finite-size scaling theory, were used to calculate the phase boundaries between the percolating and nonpercolating regions, thus determining the complete phase diagram of the system in the (p_{s},p_{b}) space. In the case of the S∩B model, the obtained results are in excellent agreement with previous theoretical and numerical predictions. In the case of the S∪B model, the limiting curve separating percolating and nonpercolating regions is reported here.

Numerical simulations and finite-size scaling analysis have been performed to study the jamming and percolation behavior of elongated objects deposited on two-dimensional honeycomb lattices. The depositing particle is modeled as a linear array of length k (so-called k-mer), maximizing the distance between first and last monomers in the chain. The separation between k-mer units is equal to the lattice constant. Hence, k sites are occupied by a k-mer when adsorbed onto the surface. The adsorption process starts with an initial configuration, where all lattice sites are empty. Then, the sites are occupied following a random sequential adsorption mechanism. The process finishes when the jamming state is reached and no more objects can be deposited due to the absence of empty site clusters of appropriate size and shape. Jamming coverage θ&#95;{j,k} and percolation threshold θ&#95;{c,k} were determined for a wide range of values of k (2≤k≤128). The obtained results shows that (i) θ&#95;{j,k} is a decreasing function with increasing k, being θ&#95;{j,k→∞}=0.6007(6) the limit value for infinitely long k-mers; and (ii) θ&#95;{c,k} has a strong dependence on k. It decreases in the range 2≤k<48, goes through a minimum around k=48, and increases smoothly from k=48 up to the largest studied value of k=128. Finally, the precise determination of the critical exponents ν, β, and γ indicates that the model belongs to the same universality class as 2D standard percolation regardless of the value of k considered.

Irreversible multilayer adsorption of semirigid k-mers on one-dimensional lattices of size L is studied by numerical simulations complemented by exhaustive enumeration of configurations for small lattices. The deposition process is modeled by using a random sequential adsorption algorithm, generalized to the case of multilayer adsorption. The paper concentrates on measuring the jamming coverage for different values of k-mer size and number of layers n. The bilayer problem (n≤2) is exhaustively analyzed, and the resulting tendencies are validated by the exact enumeration techniques. Then, the study is extended to an increasing number of layers, which is one of the noteworthy parts of this work. The obtained results allow the following: (i) to characterize the structure of the adsorbed phase for the multilayer problem. As n increases, the (1+1)-dimensional adsorbed phase tends to be a "partial wall" consisting of "towers" (or columns) of width k, separated by valleys of empty sites. The length of these valleys diminishes with increasing k; (ii) to establish that this is an in-registry adsorption process, where each incoming k-mer is likely to be adsorbed exactly onto an already adsorbed one. With respect to percolation, our calculations show that the percolation probability vanishes as L increases, being zero in the limit L→∞. Finally, the value of the jamming critical exponent ν&#95;{j} is reported here for multilayer adsorption: ν&#95;{j} remains close to 2 regardless of the considered values of k and n. This finding is discussed in terms of the lattice dimensionality.

Numerical simulations and finite-size scaling analysis have been performed to study the jamming and percolation behavior of straight semirigid rods adsorbed on two-dimensional square lattices. The depositing objects can be adsorbed on the surface forming two layers. The filling of the lattice is carried out following a generalized random sequential adsorption (RSA) mechanism. In each elementary step, (i) a set of k consecutive nearest-neighbor sites (aligned along one of two lattice axes) is randomly chosen and (ii) if each selected site is either empty or occupied by a k-mer unit in the first layer, then a new k-mer is then deposited onto the lattice. Otherwise, the attempt is rejected. The process starts with an initially empty lattice and continues until the jamming state is reached and no more objects can be deposited due to the absence of empty site clusters of appropriate size and shape. A wide range of values of k (2≤k≤64) is investigated. The study of the kinetic properties of the system shows that (1) the jamming coverage θ&#95;{j,k} is a decreasing function with increasing k, with θ&#95;{j,k→∞}=0.7299(21) the limit value for infinitely long k-mers and (2) the jamming exponent ν&#95;{j} remains close to 1, regardless of the size k considered. These findings are discussed in terms of the lattice dimensionality and number of sites available for adsorption. The dependence of the percolation threshold θ&#95;{c,k} as a function of k is also determined, with θ&#95;{c,k}=A+Bexp(-k/C), where A=θ&#95;{c,k→∞}=0.0457(68) is the value of the percolation threshold by infinitely long k-mers, B=0.276(25), and C=14(2). This monotonic decreasing behavior is completely different from that observed for the standard problem of straight rods on square lattices, where the percolation threshold shows a nonmonotonic k-mer size dependence. The differences between the results obtained from bilayer and monolayer phases are explained on the basis of the transversal overlaps between rods occurring in the bilayer problem. This effect (which we call a "cross-linking effect"), its consequences on the filling kinetics, and its implications in the field of conductivity of composites filled with elongated particles (or fibers) are discussed in detail. Finally, the precise determination of the critical exponents ν, β, and γ indicates that, although the increasing in the width of the deposited layer drastically affects the behavior of the percolation threshold with k and other critical properties (such as the crossing points of the percolation probability functions), it does not alter the nature of the percolation transition occurring in the system. Accordingly, the bilayer model belongs to the same universality class as two-dimensional standard percolation model.

We revisit the problem of excluded volume deposition of rigid rods of length k unit cells over square lattices. Two new features are introduced: (a) two new short-distance complementary order parameters, called Π and Σ, are defined, calculated, and discussed to deal with the phases present as coverage increases; (b) the interpretation is now done beginning at the high-coverage ordered phase which allows us to interpret the low-coverage nematic phase as an ergodicity breakdown present only when k≥7. In addition the data analysis invokes both mutability (dynamical information theory method) and Shannon entropy (static distribution analysis) to further characterize the phases of the system. Moreover, mutability and Shannon entropy are compared, and we report the advantages and disadvantages they present for their use in this problem.

Irreversible adsorption of objects of different shapes and sizes on Euclidean, fractal, and random lattices is studied. The adsorption process is modeled by using random sequential adsorption algorithm. Objects are adsorbed on one-, two-, and three-dimensional Euclidean lattices, on Sierpinski carpets having dimension d between 1 and 2, and on Erdős-Rényi random graphs. The number of sites is M=L^{d} for Euclidean and fractal lattices, where L is a characteristic length of the system. In the case of random graphs, such a characteristic length does not exist, and the substrate can be characterized by a fixed set of M vertices (sites) and an average connectivity (or degree) g. This paper concentrates on measuring (i) the probability W&#95;{L(M)}(θ) that a lattice composed of L^{d}(M) elements reaches a coverage θ and (ii) the exponent ν&#95;{j} characterizing the so-called jamming transition. The results obtained for Euclidean, fractal, and random lattices indicate that the quantities derived from the jamming probability W&#95;{L(M)}(θ), such as (dW&#95;{L}/dθ)&#95;{max} and the inverse of the standard deviation Δ&#95;{L}, behave asymptotically as M^{1/2}. In the case of Euclidean and fractal lattices, where L and d can be defined, the asymptotic behavior can be written as M^{1/2}=L^{d/2}=L^{1/ν&#95;{j}}, with ν&#95;{j}=2/d.

The percolation behavior of aligned rigid rods of length k (k-mers) on two-dimensional triangular lattices has been studied by numerical simulations and finite-size scaling analysis. The k-mers, containing k identical units (each one occupying a lattice site), were irreversibly deposited along one of the directions of the lattice. The connectivity analysis was carried out by following the probability R&#95;{L,k}(p) that a lattice composed of L×L sites percolates at a concentration p of sites occupied by particles of size k. The results, obtained for k ranging from 2 to 80, showed that the percolation threshold p&#95;{c}(k) exhibits a increasing function when it is plotted as a function of the k-mer size. The dependence of p&#95;{c}(k) was determined, being p&#95;{c}(k)=A+B/(C+sqrt[k]), where A=p&#95;{c}(k→∞)=0.582(9) is the value of the percolation threshold by infinitely long k-mers, B=-0.47(0.21), and C=5.79(2.18). This behavior is completely different from that observed for square lattices, where the percolation threshold decreases with k. In addition, the effect of the anisotropy on the properties of the percolating phase was investigated. The results revealed that, while for finite systems the anisotropy of the deposited layer favors the percolation along the parallel direction to the alignment axis, in the thermodynamic limit, the value of the percolation threshold is the same in both parallel and transversal directions. Finally, an exhaustive study of critical exponents and universality was carried out, showing that the phase transition occurring in the system belongs to the standard random percolation universality class regardless of the value of k considered.

Numerical simulations and finite-size scaling analysis have been carried out to study the problem of inverse site percolation by the removal of k×k square tiles (k^{2}-mers) from square lattices. The process starts with an initial configuration, where all lattice sites are occupied and, obviously, the opposite sides of the lattice are connected by occupied sites. Then the system is diluted by removing k^{2}-mers of occupied sites from the lattice following a random sequential adsorption mechanism. The process finishes when the jamming state is reached and no more objects can be removed due to the absence of occupied sites clusters of appropriate size and shape. The central idea of this paper is based on finding the maximum concentration of occupied sites, p&#95;{c,k}, for which the connectivity disappears. This particular value of the concentration is called the inverse percolation threshold and determines a well-defined geometrical phase transition in the system. The results obtained for p&#95;{c,k} show that the inverse percolation threshold is a decreasing function of k in the range 1≤k≤4. For k≥5, all jammed configurations are percolating states, and consequently, there is no nonpercolating phase. In other words, the lattice remains connected even when the highest allowed concentration of removed sites is reached. The jamming exponent ν&#95;{j} was measured, being ν&#95;{j}=1 regardless of the size k considered. In addition, the accurate determination of the critical exponents ν, β, and γ reveals that the percolation phase transition involved in the system, which occurs for k varying between one and four, has the same universality class as the standard percolation problem.

Jamming and percolation of three-dimensional (3D) k×k×k cubic objects (k^{3}-mers) deposited on simple cubic lattices have been studied by numerical simulations complemented with finite-size scaling theory. The k^{3}-mers were irreversibly deposited into the lattice. Jamming coverage θ&#95;{j,k} was determined for a wide range of k (2≤k≤40). θ&#95;{j,k} exhibits a decreasing behavior with increasing k, being θ&#95;{j,k=∞}=0.4204(9) the limit value for large k^{3}-mer sizes. In addition, a finite-size scaling analysis of the jamming transition was carried out, and the corresponding spatial correlation length critical exponent ν&#95;{j} was measured, being ν&#95;{j}≈3/2. However, the obtained results for the percolation threshold θ&#95;{p,k} showed that θ&#95;{p,k} is an increasing function of k in the range 2≤k≤16. For k≥17, all jammed configurations are nonpercolating states, and consequently, the percolation phase transition disappears. The interplay between the percolation and the jamming effects is responsible for the existence of a maximum value of k (in this case, k=16) from which the percolation phase transition no longer occurs. Finally, a complete analysis of critical exponents and universality has been done, showing that the percolation phase transition involved in the system has the same universality class as the 3D random percolation, regardless of the size k considered.

Numerical simulations and finite-size scaling analysis have been carried out to study standard and inverse bond percolation of straight rigid rods on square lattices. In the case of standard percolation, the lattice is initially empty. Then, linear bond k-mers (sets of k linear nearest-neighbor bonds) are randomly and sequentially deposited on the lattice. Jamming coverage p&#95;{j,k} and percolation threshold p&#95;{c,k} are determined for a wide range of k (1≤k≤120). p&#95;{j,k} and p&#95;{c,k} exhibit a decreasing behavior with increasing k, p&#95;{j,k→∞}=0.7476(1) and p&#95;{c,k→∞}=0.0033(9) being the limit values for large k-mer sizes. p&#95;{j,k} is always greater than p&#95;{c,k}, and consequently, the percolation phase transition occurs for all values of k. In the case of inverse percolation, the process starts with an initial configuration where all lattice bonds are occupied and, given that periodic boundary conditions are used, the opposite sides of the lattice are connected by nearest-neighbor occupied bonds. Then, the system is diluted by randomly removing linear bond k-mers from the lattice. The central idea here is based on finding the maximum concentration of occupied bonds (minimum concentration of empty bonds) for which connectivity disappears. This particular value of concentration is called the inverse percolation threshold p&#95;{c,k}^{i}, and determines a geometrical phase transition in the system. On the other hand, the inverse jamming coverage p&#95;{j,k}^{i} is the coverage of the limit state, in which no more objects can be removed from the lattice due to the absence of linear clusters of nearest-neighbor bonds of appropriate size. It is easy to understand that p&#95;{j,k}^{i}=1-p&#95;{j,k}. The obtained results for p&#95;{c,k}^{i} show that the inverse percolation threshold is a decreasing function of k in the range 1≤k≤18. For k>18, all jammed configurations are percolating states, and consequently, there is no nonpercolating phase. In other words, the lattice remains connected even when the highest allowed concentration of removed bonds p&#95;{j,k}^{i} is reached. In terms of network attacks, this striking behavior indicates that random attacks on single nodes (k=1) are much more effective than correlated attacks on groups of close nodes (large k's). Finally, the accurate determination of critical exponents reveals that standard and inverse bond percolation models on square lattices belong to the same universality class as the random percolation, regardless of the size k considered.

A generalization of the site-bond percolation problem was studied, in which pairs of neighboring sites (site dimers) and bonds are occupied irreversibly, randomly, and independently on homogeneous square surfaces. A dimer is composed of two segments and occupies two adjacent sites. Each segment can be either a conductive segment (segment type A) or a nonconductive segment (segment type B). Two types of dimers are considered, AA and AB, and the connectivity analysis is carried out by accounting only for the conductive segments (segments type A) in combination with bonds. For the combination of dimers and bonds, two different criteria were analyzed: the union or the intersection between the adsorbed percolating particles and the bonds. By means of numerical simulations and finite-size scaling analysis, the complete phase diagram separating a percolating from a non-percolating region was determined.

The orientational phase transitions that occur in the deposition of longitudinal polymers of length k (in terms of lattice units) are characterized by information theory techniques. We calculate the absolute value of an order parameter δ, which weights the relative orientations of the deposited rods, which varies between 0.0 (random orientation) and 1.0 (fully oriented in either of the two equivalent directions in an L×L square lattice). A Monte Carlo (MC) algorithm is implemented to induce a dynamics allowing for accommodation of the rods for any given density or coverage θ (ratio of the occupied sites over all the sites in the lattice). The files storing δ(t) (with time t measured in MC steps) are then treated by data recognizer wlzip based on data compressor techniques yielding the information content measured by a parameter η(θ). This allows us to recognize two maxima separated by a well-defined minimum for η(θ) provided k≥7. The first maximum is associated with an isotropic-nematic (I-N) phase transition occurring at intermediate density, while the second maximum is associated with some kind of nematic-isotropic transition at high coverage. In the cases of k<7, the curves for η(θ) are almost constant, presenting a very broad maximum which can hardly be associated with a phase transition. The study varies L and k, allowing for a basic scaling of the found critical densities towards the thermodynamic limit. These calculations confirm the tendency obtained by different methods in the case of the intermediate-density I-N phase transition, while this tendency is established here in the case of the high-density phase transition.

The deposition of one-dimensional objects (such as polymers) on a one-dimensional lattice with the presence of impurities is studied in order to find saturation conditions in what is known as jamming. Over a critical concentration of k-mers (polymers of length k), no further depositions are possible. Five different nematic (directional) depositions are considered: baseline, irreversible, configurational, loose-packing, and close-packing. Correspondingly, five jamming functions are found, and their dependencies on the length of the lattice, L, the concentration of impurities, p=M/L (where M is the number of one-dimensional impurities), and the length of the k-mer (k) are established. In parallel, numeric simulations are performed to compare with the theoretical results. The emphasis is on trimers (k=3) and p in the range [0.01,0.15], however other related cases are also considered and reported.

The percolation problem of irreversibly deposited heteronuclear dimers on square lattices is studied. A dimer is composed of two segments, and it occupies two adjacent adsorption sites. Each segment can be either a conductive segment (segment type A) or a nonconductive segment (segment type B). Three types of dimers are considered: AA, BB, and AB. The connectivity analysis is carried out by accounting only for the conductive segments (segments type A). The model offers a simplified representation of the problem of percolation of defective (nonideal) particles, where the presence of defects in the system is simulated by introducing a mixture of conductive and nonconductive segments. Different cases were investigated, according to the sequence of deposition of the particles, the types of dimers involved in the process, and the degree of alignment of the deposited objects. By means of numerical simulations and finite-size scaling analysis, the complete phase diagram separating a percolating from a nonpercolating region was determined for each case. Finally, the consistency of our results was examined by comparing with previous data in the literature for linear k-mers (particles occupying k adjacent sites) with defects.

Experimental adsorption isotherms of bovine serum albumin (BSA) adsorbed on sulfonated microspheres were described by means of two analytical models: the first is the well-known Langmuir-Freundlich model (LF), and the second, called fractional statistical theory of adsorption (FSTA), is a statistical thermodynamics model developed recently by Ramirez-Pastor et al. [Phys. Rev. Lett. 93 (2004) 186101]. The experimental data, obtained by Hu et al. [Biochem. Eng. J. 23 (2005) 259] for different concentrations of sulfonate group on the surface of the microspheres, were correlated by using a fitting algorithm based on least-squares statistics. The combination of LF and FSTA models, along with the choice of an adequate fitting procedure, allowed us to obtain several conclusions: (i) as previously reported in the literature, the maximum amount adsorbed increases as the amount of sulfonate group increases; (ii) the equilibrium constant does not appear as a sensitive parameter to the amount of sulfonate group on the surface of the microspheres; and (iii) the values of the fitting parameters obtained from FSTA may be indicative of a mismatch between the equilibrium separation of the intermolecular interaction and the distance between the adsorption sites. The exhaustive study presented here has shown that FSTA model is a good one considering the complexity of the physical situation, which is intended to be described and could be more useful in interpreting experimental data of adsorption of molecules with different sizes and shapes., (Copyright © 2012 Elsevier Inc. All rights reserved.)

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)., (© 2012 American Institute of Physics)

In the present paper, the adsorption thermodynamics of a lattice-gas model which mimics a nanoporous environment is studied by considering nonadditive interactions between the adsorbed particles. It is assumed that the energy linking a certain atom with any of its nearest neighbors strongly depends on the state of occupancy in the first coordination sphere of such an adatom. By means of Monte Carlo (MC) simulations in the grand canonical ensemble, adsorption isotherms and differential heats of adsorption were calculated. Their striking behaviors were analyzed and discussed in terms of the low temperature phases formed in the system. Finally, the results obtained from MC simulations were compared with the corresponding ones from Bragg-Williams approximation.

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, the adsorbent is modeled as one-dimensional channels of equivalent adsorption sites arranged in a triangular cross-sectional structure. Two kinds of lateral interaction energies have been considered: (1) w(L) interaction energy between nearest-neighbor particles adsorbed along a single channel and (2) w(T) interaction energy between particles adsorbed across nearest-neighbor channels. We focus on the case of repulsive transverse (w(T)>0) and attractive longitudinal (w(L)<0) lateral interactions, where a rich variety of structural orderings are observed in the adlayer depending on the value of the parameters k(B)T/w(T) (being k(B) the Boltzmann constant) and w(L)/w(T). The results reveal the existence of a first-order phase transition in the adlayer between a low-temperature "condensed" phase and a high-temperature "disordered" phase.

In this work we study a simple model of multilayer adsorption of noninteracting polyatomic species on homogeneous and heterogeneous surfaces. A new approximate analytic isotherm is obtained and validated by comparing with Monte Carlo simulation in one- and two-dimensional lattices. Then, we use the well-known Brunauer-Emmet-Teller (BET) approach to analyze these isotherms and to estimate the monolayer volume, v(m). In this way, we confirm previous observations that the value of the v(m) obtained by the BET equation depends strongly on adsorbate size and surface heterogeneity. In all cases, we find that the use of the BET equation leads to an underestimate of the true monolayer capacity. Nevertheless, a compensation effect is found for the adsorption on a patchwise bivariate surface, but this is not enough to eliminate the decrease of v(m) caused by the molecular size. In addition, we consider also the possibility to use the model to study the adsorption on nanotube bundles.

In the present paper, the multicomponent adsorption of polyatomic species is described as a fractional statistics problem, based on Haldane's statistics. Site exclusion is characterized by a "mutual exclusion matrix" g, which relates to the sizes of the different species and lattice geometry. The adsorption process has been monitored through total and partial isotherms, energy of adsorption and configurational entropy of the adsorbed phase. The thermodynamic functions calculated for a monomer-dimer mixture were applied to describe the adsorption of methane-ethane mixtures in zeolites. In the case of zero lateral interactions, the present approach was compared to the well-known ideal adsorbed solution theory. The results show that the treatment of this complex problem can be significantly simplified if looked up from the new theoretical perspective.

The adsorption of gases on patchwise heterogeneous bivariate surfaces is studied. These surfaces are characterized by a collection of strong and weak adsorbing patches with a typical length scale l. Different forms and spatial arrangements of these patches determine different topographies characterized by an effective length, l(eff) = sigmal, where sigma takes values from 1 to 4 for the different topographies considered here. Previous studies showed that the mean square deviation between isotherms corresponding to different values of l(eff) scaled as a power law with exponent alpha, without providing any physical interpretation of such behavior. In the present work, we introduce a different scaling function, chi(l), which is shown to be twice the difference in free energy per site between a reference isotherm and the given isotherm, at half coverage. With this function the scaling behavior and the value of the scaling exponent alpha are determined over the whole range of interparticles interaction energy and adsorptive energy, and for different temperatures, through Monte Carlo simulations. The results are similar to those obtained in previous studies, with a value of alpha which is half the one obtained before due to the different definition of the scaling function, but the present analysis provides a full understanding of the scaling behavior based on the physical significance of the scaling function and the scaling exponent.

In this paper, the percolation of (a) linear segments of size k and (b) k-mers of different structures and forms deposited on a square lattice contaminated with previously adsorbed impurities have been studied. The contaminated or diluted lattice is built by randomly selecting a fraction of the elements of the lattice (either bonds or sites) which are considered forbidden for deposition. Results are obtained by extensive use of finite size scaling theory. Thus, in order to test the universality of the phase transition occurring in the system, the numerical values of the critical exponents were determined. The characteristic parameters of the percolation problem are dependent not only on the form and structure of the k-mers but also on the properties of the lattice where they are deposited. A phase diagram separating a percolating from a nonpercolating region is determined as a function of the parameters of the problem. A comparison between random site and random bond percolation in the presence of impurities on the lattice is presented.

In the present paper, the connection between surface order-disorder phase transitions and the percolating properties of the adsorbed phase has been studied. For this purpose, four lattice-gas models in the presence of repulsive interactions have been considered. Namely, monomers on honeycomb, square, and triangular lattices, and dimers (particles occupying two adjacent adsorption sites) on square substrates. By using Monte Carlo simulation and finite-size scaling analysis, we obtain the percolation threshold theta(c) of the adlayer, which presents an interesting dependence with w/k(B)T (w, k(B), and T being the lateral interaction energy, the Boltzmann constant, and the temperature, respectively). For each geometry and adsorbate size, a phase diagram separating a percolating and a nonpercolating region is determined.

The configurational entropy of interacting particles adsorbed on one-dimensional channels arranged in a triangular cross-sectional structure is studied by combining Monte Carlo simulation and thermodynamic integration method. Three different energies have been considered in the adsorption process: (1) epsilono, constant interaction energy between a monomer and an adsorption site; (2) wL, interaction energy between nearest-neighbor particles adsorbed along a single channel, and (3) wT, interaction energy between particles adsorbed across nearest-neighbor channels. Special attention is devoted to the case of repulsive transversal interactions (wT>0), for which a rich variety of ordered phases are observed in the adlayer, depending on the value of the parameters kBT/wT (being kB the Boltzmann constant) and wL/wT. The influence of each ordered structure on the configurational entropy of the adlayer has been analyzed and discussed in the context of the lattice-gas model.