Adsorption thermodynamics of a lattice-gas model with non-additive lateral interactions on triangular and honeycomb lattices

Adsorption thermodynamics of a lattice-gas model with non-additive interactions between adsorbed particles for triangular and honeycomb lattices is discussed in the present study. The model used here assumes that the energy which links a certain atom with any of its nearest-neighbors strongly depends on the state of occupancy in the first coordination sphere of that adatom. By means of Monte Carlo simulations in the grand canonical ensemble the adsorption isotherms and isothermal susceptibility (or equivalently the mean square density fluctuations of adparticles) were calculated and their striking behavior was analyzed and discussed in terms of the low temperature phases formed in the system.     

Modeling multilayer adsorption of interacting polyatomic species on heterogeneous surfaces

In the present work, a generalized lattice-gas model to study multilayer adsorption of interacting polyatomic species on heterogeneous surfaces is introduced. Using an approximation in the spirit of the well-known Brunauer-Emmet-Teller (BET) model, a new theoretical isotherm is obtained in one- and two-dimensional lattices and compared with Monte Carlo simulation. In addition, the BET approach is used to analyze these isotherms and to estimate the monolayer volume. In all cases, the application of the BET equation leads to an underestimate of the true monolayer capacity. However, significant compensation effects were observed for heterogeneous surfaces and attractive lateral interactions.     

Adsorption in one-dimensional channels arranged in a triangular structure: Theory and Monte Carlo simulations

Adsorption thermodynamics of interacting particles adsorbed on one-dimensional channels arranged in a triangular cross-sectional structure is studied through Bragg-Williams approximation (BWA), Monte Carlo (MC) simulations and the recently reported Effective Substates approximation (ESA) [J.L. Riccardo, G. Zgrablich, W. A. Steele, Appl. Surf. Sci. 196 (2002) 138]. 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 transversal interactions (w_T>0), for which a rich variety of ordered phases are observed in the adlayer, depending on the value of the parameters k_BT/w_T (being k_B the Boltzmann constant) and w_L/w_T. Comparisons between analytical data and MC simulations are performed in order to test the validity of the theoretical models. Appreciable differences can be seen for the different approximations, ESA being the most accurate for all cases.     

Diffusion of interacting particles in one-dimensional heterogeneous systems

The equilibrium and transport properties of interacting ad-particles on bivariate heterogeneous chains are studied by combining analytical and simulation approaches. Heterogeneity is introduced in the way of patches of shallow and deep adsorbing sites distributed in a deterministic alternating way. Adsorption isotherms and mean-square fluctuations of the surface coverage, as well as the jump and collective diffusion coefficients, are calculated for different values of lateral interactions between ad-particles and substrate heterogeneity. In addition, different elementary jump mechanisms are introduced and their influence in the coverage dependence of the collective diffusion coefficient is investigated.     

Tracer diffusion of dimers on correlated heterogeneous surfaces

The diffusion of a single dimer adsorbed on highly correlated heterogeneous substrates is studied through Monte Carlo simulations. The topography has been characterized by patches of weak and strong adsorbing sites, arranged in a chessboard-like ordered structure. The time behavior of the mean-square displacement of the dimer is analyzed for different temperatures and patch size. Based on this analysis, a possible method for the characterization of the correlated heterogeneous topography from dimer diffusion measurements is discussed.     

Monte Carlo simulation of metal deposition on foreign substrates

The deposition of a metal on a foreign substrate is studied by means of grand canonical Monte Carlo simulations and a lattice-gas model with pair potential interactions between nearest neighbors. The influence of temperature and surface defects on adsorption isotherms and differential heat of adsorption is considered. The general trends can be explained in terms of the relative interactions between adsorbate atoms and substrate atoms. The systems Ag/Au(1 0 0), Ag/Pt(1 0 0), Au/Ag(1 0 0) and Pt/Ag(1 0 0) are analyzed as examples.     

Percolation of interacting particles on heterogeneous surfaces

The percolation problem of interacting particles on square lattices with two kinds of energetically different sites is studied. Square lattices formed by collections of either randomly or orderly distributed sites are generated. The system is characterized by two parameters, namely, the interaction between adjacent particles, ω, and the energy difference between the two kinds of sites, . Particles are adsorbed at equilibrium on the lattice. By means of Monte Carlo simulations and finite-size scaling analysis the critical coverage is determined. The percolative behavior of the system is presented and discussed in terms of the mentioned parameters, ω and .     

The effect of three-body interactions on thermal desorption spectra

Thermal desorption spectra are calculated for a one-dimensional chain and for a two-dimensional square lattice using the transfer-matrix technique and Monte Carlo simulations. Lateral interactions of adsorbed particles cause a splitting of spectra. The repulsive three-body interactions are shown to lead to an inequality of the integral intensities of the thermal desorption peaks.     

Diffusion-limited aggregates grown on nonuniform substrates

In the present paper, patterns of diffusion-limited aggregation (DLA) grown on nonuniform substrates are investigated by means of Monte Carlo simulations. We consider a nonuniform substrate as the largest percolation cluster of dropped particles with different structures and forms that occupy more than a single site on the lattice. The aggregates are grown on such clusters, in the range the concentration, p$p$, from the percolation threshold, _pc$p_c$ up to the jamming coverage, _pj$p_j$. At the percolation threshold, the aggregates are asymmetrical and the branches are relatively few. However, for larger values of p$p$, the patterns change gradually to a pure DLA. Tiny qualitative differences in this behavior are observed for different k$k$ sizes. Correspondingly, the fractal dimension of the aggregates increases as p$p$ raises in the same range _pc≤p≤_pj$p_c\le p\le p_j$. This behavior is analyzed and discussed in the framework of the existing theoretical approaches.     

The effect of NO/O2 ratio in NO-CO-O2 reaction on a catalytic surface: A computer simulation study

The interaction among the reacting species in the NO-CO-O₂ reaction on a metal catalytic surface that proceeds according to the Langmuir-Hinshelwood mechanism is studied by means of Monte Carlo simulation. The study of this three-component system is essential for the understanding of the influence of NO/O₂ ratio on the catalytic reduction of NO into N & O and oxidation of CO to CO₂. It is found that this complex system, which has not been studied on these lines before, exhibits irreversible phase transitions between active states with sustained reaction and poisoned states with the catalytic surface fully covered by the reactants. The phase diagrams of the surface coverage with CO, N or O and the steady state production of CO₂ are evaluated as a function of the partial pressure of CO in the gas phase. From this study, it is observed that with the addition of NO in the CO-O₂ reaction, the critical points in the phase diagram move towards lower values of CO partial pressure but the width of reaction window remains almost the same. However, the maximum production rate of CO₂ decreases continuously. On the other hand, the addition of O₂ in the NO-CO reaction shifts the critical points towards higher values of CO pressure. Moreover, the width of reaction window as well as the production rate of CO₂ increases with the increase in O₂ concentration.     

Configurational entropy of adsorbed rigid rods: Theory and Monte Carlo simulations

The configurational entropy of straight rigid rods of length k (k-mers) adsorbed on square, honeycomb, and triangular lattices is studied by combining theory and Monte Carlo (MC) simulations in grand canonical and canonical ensembles. Three theoretical models to treat k-mer adsorption on two-dimensional lattices have been discussed: (i) the Flory-Huggins approximation and its modification to address linear adsorbates; (ii) the well-known Guggenheim-DiMarzio approximation; and (iii) a simple semi-empirical model obtained by combining exact one-dimensional calculations, its extension to higher dimensions and Guggenheim-DiMarzio approach. On the other hand, grand canonical and canonical MC calculations of the configurational entropy were obtained by using a thermodynamic integration technique. In the second case, the method relies upon the definition of an artificial Hamiltonian associated with the system of interest for which the entropy of a reference state can be exactly known. Thermodynamic integration is then applied to calculate the entropy in a given state of the system of interest. Comparisons between MC simulations and theoretical results were used to test the accuracy and reliability of the models studied.     

Impact of orientational distribution of adsorbing objects on dynamics of Random Sequential Ballistic Adsorption (RSBA) dynamics

Recently, by proposing a new variant of Random Sequential Adsorption (RSA) namely Random Sequential Ballistic Adsorption (RSBA) model [Pradip B. Shelke, A.G. Banpurkar, S.B. Ogale, A.V. Limaye, Surf. Sci. 601 (2007) 274], we addressed the issue of adsorption dynamics of extended objects where the objects, upon adsorption, protrude outside the substrate. This study brought out the role of the arriving trajectory in the adsorption dynamics. In the present work the possible role of the orientational distribution of the arriving objects in the RSBA dynamics is investigated. The dynamics of RSBA of needles (line segments) is studied analytically and by computer simulation for different types of θ distributions of arriving needles, θ being the angle made by the arriving needle with normal to the substrate. Three types of θ distributions, namely a uniform distribution over the range (0, π/2), a Gaussian distribution and a distribution uniform over the solid angle, are considered. Analytical treatment establishes that in all the three cases, the number n(t) of adsorbed objects at a late time t follows a power law n(t) ∼ t^α, and the exponent α depends on the specifics of the θ distribution. In general, for distribution f(θ) ∝ θ^β, for θ → 0, α is found to be 2/(β + 3). The simulation results are in excellent agreement with the analytical findings and together they reveal that the orientational distribution of arriving objects has significant consequences for the Random Sequential Ballistic Adsorption (RSBA) process.     

Adsorption thermodynamics of monomers on diluted-bonds triangular lattices

The surface of amorphous solids cannot be usually represented by a regular lattice of adsorbing sites. One of the main characteristics of such surfaces is a variable connectivity for each site. A simple model consisting of a triangular lattice where a fraction of bonds (interactions) is suppressed at random is used here to find out, by using Monte Carlo simulations, how the adsorption thermodynamics of repulsively interacting monomers is modified with respect to the same process in the regular lattice. Adsorption isotherm, differential heat of adsorption and adsorbed phase entropy calculations are carried out showing and interpreting the effects of the variable connectivity. In particular, it is found that the order-disorder phase transition observed for the regular lattice survives, though with modifications, above a critical mean connectivity.     

Monte Carlo model of CO adsorption on supported Pt nanoparticle

For molecular simulations with thousands of atoms it is desirable to use a lattice gas model because it is fast and easy-to-use for computations. Unfortunately, simulation of adsorption on heterogeneous surfaces within this model is rather complicated due to a large variety of available adsorption site types. We propose the combined model with lattice representation of adsorbent atoms and arbitrary location of adsorbate atoms. Using this model simulation of CO adsorption on supported Pt nanoparticles has been performed. With the proposed approach the above-mentioned difficulties were successfully overcome.     

Study of the adsorption of interacting dimers on square lattices by using a cluster-exact approximation

A theoretical approach, based on exact calculation of the partition function on finite rectangular clusters, is introduced to study the adsorption of interacting homonuclear dimers on square lattices. An efficient algorithm allows us to calculate the detailed structure of the configuration space for m=(k×l) clusters with m varying from 8 to 48. The adsorption process has been monitored by following thermodynamic properties such as coverage versus chemical potential, internal energy and specific heat of the adlayer, etc. The analytical results are compared with those in [Surf. Sci. 411 (1998) 294], which were obtained by using Monte Carlo simulation and finite-size scaling techniques. The theoretical adsorption isotherms and phase diagrams (critical temperature versus coverage) for both attractive and repulsive lateral interactions are in good qualitative agreement with the computational data. This agreement between simulated and theoretical results supports the validity of the cluster-exact approximation proposed in this paper.     

水在二氧化钚表面吸附行为的模拟

采用Kinetic Monte Carlo方法对水在PuO₂表面的吸附行为进行数值模拟研究,通过对Statebake,Haschke等的实验数据进行数值拟合得到水的脱附活化能:0~0.5层为200 kJ·mol^-1,0.5~1层为135 kJ·mol^-1,1~2层为47·6 kJ.mol^-1,2~3层为43.8 kJ·mol^-1,3层以后为41.1 kJ·mol^-1;采用这些参数对不同升温速率下的热脱附谱以及不同温度、水分压下的吸附等温线和等压线进行预测.     

Experimental, density function theory calculations and molecular dynamics simulations to investigate the adsorption of some thiourea derivatives on iron surface in nitric acid solutions

The effects of thiourea derivatives, namely N-methyl thiourea (MTU), N-propyl thiourea (PTU) and N-allyl thiourea (ATU) on the corrosion behaviour of iron in 1.0 M solution of HNO₃ have been investigated in relation to the concentration of thiourea derivatives. The experimental data obtained using the techniques of weight loss, Tafel polarization and electrochemical impedance spectroscopy, EIS. The results showed that these compounds revealed a good corrosion inhibition, (ATU) being the most efficient and (MTU) the least. Computational studies have been used to find the most stable adsorption sites for thiourea derivatives. This information help to gain further insight about corrosion system, such as the most likely point of attack for corrosion on iron (1 1 0), the most stable site for thiourea derivatives adsorption and the binding energy of the adsorbed layer. The efficiency order of the inhibitors obtained by experimental results was verified by theoretical analysis.