A non-thermal lattice gas model for a dimer-trimer reaction on a catalytic surface: A computer simulation study

The kinetics of an irreversible dimer-trimer reaction of the type 3A₂ + 2B₃ → 6AB have been studied using a non-thermal (precursor mechanism) model on a square as well as on a hexagonal lattice surface by Monte Carlo simulation. When the range of the precursors (A atoms) is increased, the model gives production rates (reactive window widths) that are quite large as compared with those for thermal (Langmuir-Hanshelwood mechanism) model. The phase diagrams qualitatively resemble with the standard ZGB model except that the continuous transition point is eliminated when the range of the precursors is extended up to the third nearest neighbourhood. The diffusion of A atoms on the surface as well as their desorption from the surface with a certain probability is also considered to see their effects on the reaction mechanism.     

CO-H2-O2 reaction on a catalytic surface: A computer simulation study

The oxidation of carbon monoxide to form carbon dioxide and the oxidation of hydrogen to form water are the reactions of environmental and industrial importance. These two reactions have been studied independently by Monte Carlo computer simulation using Langmuir-Hinshelwood mechanism but no effort has been made to study the combined CO-H₂-O₂ reaction on these lines. Keeping in view the importance of this 3-component system, the surface coverages and production rates are studied as a function of CO partial pressure for different ratios of H₂ and O₂. The diffusion of reacting species on the surface as well as their desorption from the surface is also introduced to include temperature effects. The phase diagrams of the system are drawn to observe the behavior of these atoms/molecules on the surface and the production of CO₂ and H₂O are determined at different concentrations of H₂. The results are compared with 2-component systems.     

Effect of the Eley-Rideal step on catalytic oxidation of CO under periodic external pressure

The effect of periodic variation of external pressure on the catalytic oxidation of CO is simulated for a modified Ziff-Gulari-Barshad (ZGB) model including the Eley-Rideal (ER) step. The external CO partial pressure is periodically varied between its values in reactive and CO poisoned states. The results show different amplitudes of such perturbation significantly influence the CO₂ production rate. Latter also changes with the period of such oscillations, especially for perturbations with larger amplitudes. However, for a given period there is a critical value of the amplitude above which, the catalyst surface becomes irreversibly poisoned.     

Study of oscillations and pattern formation in the CO + O2 reaction on Pt(1 0 0) surfaces through dynamic Monte Carlo simulation

Oscillations and pattern formation driven by a surface reconstruction are studied for the catalytic oxidation of CO on Pt(1 0 0) single-crystal surfaces through dynamic Monte Carlo simulations at low pressure and relatively high temperatures conditions. Sustained, modulated, irregular and damped oscillations are observed in our analysis as well as the formation of cellular, target, double spiral, spiral wave and turbulent patterns. The effect and the importance of the hex ? 1 × 1 surface phase transition and partial pressure of the reactants in the gas phase on the behavior of the system are discussed.     

Phase diagrams and magnetic properties of CaCu3Fe2Os2O12 quadruple perovskite: Monte Carlo study

In this paper, a Monte Carlo Simulation (MCS) has been used to study the quadruple perovskite oxide CaCu₃Fe₂Os₂O₁₂. The system has been conceived as a mixture of atoms with the magnetic moments Cu (±1/2), Fe (±5/2, ±3/2, ±1/2) and Os (±3/2, ±1/2). Phase diagrams depending on reduced exchange couplings and reduced crystal fields have been established. A stable ferromagnetic phase at the ground state has been found. Investigation of magnetic properties has been focused on the finite size analysis of magnetization and magnetic susceptibility according to reduced temperatures. Critical temperature has been calculated through simulation and the compound has been found to belong in the three-dimensional Ising model universality class.     

铁电磁体Pb(Fe1/2Nb1/2)O3的磁电性能研究

对铁电磁体Pb(Fe_1/2Nb_1/2)O₃单晶样品中的 介电和磁性能进行了研究. 认为在其反铁磁相变点观察到的介电常数和损耗的异常来自于自发极化序和自旋序的相互作用 引起的磁电耦合. 磁矩与温度的关系曲线在Nel点以下的低温段呈上升趋势，测得的磁滞 回线证明有弱铁磁性出现. 对铁电磁体磁电相互作用的Monte Carlo模拟得到与实验类似的 结果. 关键词： 铁电磁体 1/2Nb_1/2)O₃')" href="#">Pb(Fe_1/2Nb_1/2)O₃ 磁电耦合 Monte Carlo模拟     

The catalytic reduction of NO by H2 on Ru(0 0 0 1): Observation of NHads species

Adsorption of NO and the reaction between NO and H₂ were investigated on the Ru(0 0 0 1) surface by X-ray photoelectron spectroscopy (XPS). Surface composition was measured after NO adsorption and after the selective catalytic reduction of nitric oxide with hydrogen in steady-state conditions at 320 K and 390 K in a 30:1 mixture of H₂ and NO (total pressure = 10⁻⁴ mbar). After steady-state NO reduction, molecularly adsorbed NO in both the linear on-top and threefold coordinations, NH_ads and N_ads species were identified by XPS. The coverage of the NH_ads and N_ads species was higher after the reaction at 390 K than the corresponding values at 320 K. Strong destabilisation of N_ads by O_ads was detected. A possible reaction mechanism is discussed.     

Imidazole ligand effect on O2 interaction with metalloporphyrins

We investigate the imidazole ligand effect on O₂ interaction with metalloporphyrins (MPs) using ab initio density functional calculations. We select iron-porphyrin (FeP) and cobalt-porphyrin (CoP) as MPs, and compare MP with (imidazole)MP [(Im)MP] including their O₂ adducts. The O-O bond of (Im)MP-O₂ tends to be weaker than that of MP-O₂ due to more accessible back-donation to O₂, resulting from a strong electron push from the imidazole ligand, though the effect is not true for the interaction of excited singlet O₂.     

Reactivity of (H)(e) color centers at the MgO surface: formation of O2 and N2 radical anions

We have considered the interaction of O₂ and N₂ molecules with electrons trapped at the surface of MgO by performing embedded cluster DFT calculations. Trapped electrons at the surface of MgO react instantaneously with O₂ and N₂ leading to the formation of the corresponding O₂⁻ and N₂⁻ molecular anions stabilized at specific surface sites. So far, the atomistic model for this process was based on the idea that the electrons are trapped at oxygen vacancies, the F_S⁺ centers. Recently, it has been shown that morphological sites at the MgO surface like a reverse corner, a step or a corner, can adsorb hydrogen and stabilize (H⁺)(e⁻) pairs giving rise to a new class of paramagnetic color centers. Here we show that these centers exhibit reactivity towards O₂ and N₂, which is fully consistent with the experimental observations, providing further support to the new model of electron traps at the MgO surface.     

Post-sintering annealing effect on the diffuse phase transition in (Pb1−xBax)(Yb0.5Ta0.5)O3 ceramics

The effect of post sintering annealing on the dielectric response of (Pb_1−xBa_x)(Yb_0.5Ta_0.5)O₃ ceramics in the diffuse phase transition range (x=0.2) has been investigated. The samples are prepared by conventional solid-state reaction method. The samples are sintered at 1300 °C for 2 h and annealed at different temperatures (800, 900 and 1000 °C) for 8 h and at 800 °C for different time durations (8, 12 and 24 h). A significant change in the dielectric response has been observed in all the samples. The dielectric constant increases remarkably and the dielectric loss tangent decreases. The dielectric peaks of the annealed samples are observed to be more diffused with noticeable frequency dispersion compared to the as sintered sample.     

Magnetocaloric effect and magnetic properties in NdMnO3 perovskite: A Monte Carlo approach

The magnetic properties and magnetocaloric effect in $\text{NdMn}{\text{O}}_3$ have been investigated, as well as the effect of magnetic anisotropy in the magnetocaloric properties of the perovskite-type compound. A classical Heisenberg Hamiltonian with nearest and next-nearest neighbors interactions was implemented. Hamiltonian parameters were fitted in order to reproduce experimental results. Magnetic field dependence on the magnetization, for isothermal processes, was performed. In this way, the magnetic entropy change $\left(\mathrm{\Delta }{S}_m\right)$ was computed as well as the relative cooling power (RCP). Results show that as the magnetic anisotropy constant increases, there was not only a sharpening, but also an increase in peak height of $?\mathrm{\Delta }{S}_m$. Finally, the magnetic field and anisotropy dependences on the RCP were obtained, showing that the highest values of the RCP were found for low anisotropy values.     

Electron behaviour in CH4／H2 gas mixture in electron-assisted chemical vapour deposition

The behaviour of electrons in CH_{4}/H_{2} gas mixture in electron-assisted chemical vapour deposition of diamond is investigated using Monte Carlo simulation. The electron drift velocity in gas mixture is obtained over a wide range of E/P (the ratio of the electric field to gas pressure) from 1500 to 300000 (V/m kPa^{-1}). The electron energy distribution and average energy under different gas pressure (0.1－20kPa) and CH_{4} concentration (0.5%－10.0%) are calculated. Their effects on the diamond growth are also discussed. It is believed that these results will be helpful to the selection of optimum experimental conditions for high quality diamond film deposition.     

The phase diagrams of a finite superlattice with disordered interface: A Monte Carlo study

Monte Carlo Simulation (MCS) has been used to study critical and compensation behavior of a ferrimagnetic superlattice on a simple cubic lattice. The superlattice consists of k unit cells, where the unit cell contains L layers of spin −1/2 A atoms, L layers of spin −1 B atoms and a disordered interface in between that is characterized by a random arrangement of A and B atoms of A_pB_1−p type and a negative A-B coupling. We investigate the finite and the infinite superlattices and we found that the existence and the number of the compensation points depend strongly on the thickness of the superlattice (number of unit cells).     

Density functional study of the chemisorption of O2 on the armchair surface of graphite

The reaction between O₂ and the armchair surface of a model graphite molecule has been studied using density functional calculations at the B3LYP/6-31G(d) level of theory. Both equilibrium and transition state geometries were optimized to provide a fundamental understanding of the energetics and kinetics of the chemisorption, desorption, rearrangement, and migration reactions that contribute to carbon gasification. A small barrier of 18 kJ mol⁻¹ was found for the chemisorption reaction, which is 578 kJ mol⁻¹ exothermic overall, producing a stable quinone. A number of reaction pathways with barriers below 578 kJ mol⁻¹ were characterized. Gasification of carbon occurs as CO, with barriers of 296 and 435 kJ mol⁻¹ for the first and second CO loss, respectively. The stable quinone can also undergo a rearrangement reaction to form two ketene groups, with a barrier of 260 kJ mol⁻¹. If the armchair edge is extended to include an adjacent aromatic ring, the oxide can migrate along the surface. This initially forms a furan-like bridge structure, with a barrier of just 89 kJ mol⁻¹. A further barrier of 383 kJ mol⁻¹ leads to CO desorption from the furan. The furan can also rearrange further with a barrier of 212 kJ mol⁻¹ to form a five-membered lactone, the most stable structure identified on the potential energy surface. Rearrangement and migration reactions, which have not generally been incorporated into carbon gasification models, are shown to be potentially important pathways in carbon oxidation reactions.     

一种晶体表面水平纳米线生长机理的蒙特卡罗模拟研究

采用动力学蒙特卡罗方法模拟,发现在较低过饱和度流体中对称性破缺的简单立方晶体光滑（001）表面上基于晶核的水平纳米线的生长机理．在此基础上,进一步研究了各向异性的表面上经向和纬向热粗糙度对纳米线形貌的影响,分析了纳米线的生长随时间的变化,并系统讨论了纳米线生长速率与表面经向和纬向热粗糙度、过饱和度、晶面尺寸以及表面扩散作用的依赖关系．     

Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl

New triethylammonium salts: [(C₂H₅)₃NH]SbCl₆ (TCA) and [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P2₁/n and P2₁/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C₂H₅)₃NH]SbCl₆ consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.     

Study of magnetic properties of La2/3Sr1/3MnO3 nanotubes by Monte Carlo simulation

Magnetic properties of a single nanotube whose walls are constituted by nanograins of La_2/3Sr_1/3MnO₃ are studied by means of Monte Carlo (MC) simulation. The system is considered as composed by ferromagnetic grains which couple via dipolar interaction. The grain size distribution is obtained from experimental measurements and the inter-grain distance distribution is obtained from a study of distance distribution among magnetic particles distributed in the tube walls. We show the magnetization behavior for a tube of 700 nm of diameter and 3.5 μm length. We discuss the simulation for different temperatures and external fields. As a main result, we show that the distribution of inter-granular distances has a unique behavior for tubular structures of similar diameter/length aspect ratio, independent of their sizes. This scaling relation allows us to perform the simulations using a tube of smaller dimensions. We succeed in explaining the magnetization curves, finding that dipolar interaction is necessary to explain the experimental behavior and that the grains behave as having magnetic dead layers.     

The possible role of intermediate NH species in oscillations of the NO+H2 reaction on noble metal surfaces

A comparative study of the thermodynamic properties of adsorbed NH_n species (n = 0, 1, 2, 3) on transition metal surfaces is performed by using the semi-empirical method of interacting bonds. The principal difference between single crystal surfaces exhibiting oscillatory behavior in the NO+H₂ reaction, and those surfaces which do not show such a behavior is that the combination reaction of NH species can easily proceed in the former case, whereas it is substantially endothermic on the latter surfaces.A trigger-like route for the oscillatory behavior is considered where the combination reaction of NH species operates as a temporary reaction pathway. This pathway practically does not contribute to the N₂ formation until the nitrogen coverage reaches some critical value, which ensures a sufficiently close distance between adjacent NH particles. The trigger pathway starts upon reaching that stage initiating the surface wave propagation, and stops immediately when the wave propagation is completed. The surface becomes then nearly clean and ready for the next oscillatory cycle. In this way, the feedback mechanism and the critical point of the regular wave initiation can be understood without any further assumptions. An alternative key reaction is also considered.     

Monte Carlo study of the critical behavior and magnetic properties of La2/3Ca1/3MnO3 thin films

Critical exponents offer important information concerning the interaction mechanisms near the paramagnetic to ferromagnetic transition. In this work a Monte Carlo-Metropolis simulation of the critical behavior in La_2/3Ca_1/3MnO₃ thin films is addressed. Canonical ensemble averages for magnetization per site, magnetic susceptibility and specific heat of stoichiometric manganite within a three-dimensional classical Heisenberg model with nearest magnetic neighbor interactions are computed. The La_2/3Ca_1/3MnO₃ thin films were simulated addressing the thickness influence and thermal dependence. In the model, Mn magnetic ions are distributed on a simple cubic lattice according to the perovskite structure of this manganite. Ferromagnetic coupling for the bonds Mn³⁺-Mn³⁺(e_g-e_g′), Mn³⁺-Mn⁴⁺(e_g-d³) and Mn³⁺-Mn⁴⁺(e_g′-d³) were taken into account. On the basis of finite-size scaling theory, our best estimates of critical exponents, linked to the ferromagnetic to paramagnetic transition, for the correlation length, specific heat, magnetization and susceptibility are, respectively: v=0.56±0.01, α=0.16±0.03, β=0.34±0.04γ and γ=1.17±0.05. These theoretical results are consistent with the Rushbrooke equalitiy α+2β+γ=2.