RESUMO

We present results of kinetic Monte Carlo simulations of a modified Ziff-Gulari-Barshad model for the reaction CO+O → CO(2) on a catalytic surface. Our model includes impurities in the gas phase, CO desorption, and a modification known to eliminate the unphysical O poisoned phase. The impurities can adsorb and desorb on the surface, but otherwise remain inert. In a previous work that did not include CO desorption [Buendía and Rikvold, Phys. Rev. E 85, 031143 (2012)], we found that the impurities have very distinctive effects on the phase diagram and greatly diminish the reactivity of the system. If the impurities do not desorb, once the system reaches a stationary state, the CO(2) production disappears. When the impurities are allowed to desorb, there are regions where the CO(2) reaction window reappears, although greatly reduced. Following experimental evidence that indicates that temperature effects are crucial in many catalytic processes, here we further analyze these effects by including a CO desorption rate. We find that the CO desorption has the effect to smooth the transition between the reactive and the CO rich phase, and most importantly it can counteract the negative effects of the presence of impurities by widening the reactive window such that now the system remains catalytically active in the whole range of CO pressures.

RESUMO

We study by kinetic Monte Carlo simulations the catalytic oxidation of carbon monoxide on a surface in the presence of contaminants in the gas phase. The process is simulated by a Ziff-Gulari-Barshad (ZGB) model that has been modified to include the effect of the contaminants and to eliminate an unphysical oxygen poisoned phase at very low CO partial pressures. The impurities can adsorb and desorb on the surface but otherwise remain inert. We find that if the impurities cannot desorb, no matter how small their proportion in the gas mixture, the reactive window and discontinuous transition to a CO poisoned phase at high CO pressures that characterize the original ZGB model disappear. The coverages become continuous, and once the surface has reached a steady state there is no production of CO(2). This is quite different from the behavior of systems in which the surface presents a fixed percentage of impurities. When the contaminants are allowed to desorb, the reactive phase appears again for CO pressures below a value that depends on the proportion of contaminants in the gas and on their desorption rate.

Assuntos

RESUMO

We perform Monte Carlo simulations in order to study the magnetic properties of the mixed spin-S = ± 3/2, ± 1/2 and spin-σ = ± 5/2, ± 3/2, ± 1/2 Ising model. The spins are alternated on a square lattice such that S and σ are nearest neighbors. We found that when the Hamiltonian includes antiferromagnetic interactions between the S and σ spins, ferromagnetic interactions between the spins S, and a crystal field, the system presents compensation temperatures in a certain range of the parameters. The compensation temperatures are temperatures below the critical point where the total magnetization is zero, and they have important technological applications. We calculate the finite-temperature phase diagrams of the system. We found that the existence of compensation temperatures depends on the strength of the ferromagnetic interaction between the S spins.

Assuntos

RESUMO

We study the effect of coadsorption of CO and O on a Ziff-Gulari-Barshad model with CO desorption for the reaction CO + O --> CO(2) on a catalytic surface. Coadsorption of CO at a surface site already occupied by an O is introduced by an Eley-Rideal-type mechanism that occurs with probability p, 0 < or = p < or = 1. We find that besides the well-known effect of eliminating the second-order phase transition between the reactive state and an O-poisoned state, the coadsorption step has a profound effect on the transition between the reactive state and the CO-poisoned state. The coexistence curve between these two states terminates at a critical value k(c) of the desorption rate k, which now depends on p. Our Monte Carlo simulations and finite-size scaling analysis indicate that k(c) decreases with increasing values of p. For p = 1, there appears to be a sharp phase transition between the two states only for k at (or near) zero.

RESUMO

We study the dynamical response of a two-dimensional Ising model subject to a square-wave oscillating external field. In contrast to earlier studies, the system evolves under a so-called soft Glauber dynamic [Rikvold and Kolesik, J. Phys. A 35, L117 (2002)], for which both nucleation and interface propagation are slower and the interfaces smoother than for the standard Glauber dynamic. We choose the temperature and magnitude of the external field such that the metastable decay of the system following field reversal occurs through nucleation and growth of many droplets of the stable phase, i.e., the multidroplet regime. Using kinetic Monte Carlo simulations, we find that the system undergoes a nonequilibrium phase transition, in which the symmetry-broken dynamic phase corresponds to an asymmetric stationary limit cycle for the time-dependent magnetization. The critical point is located where the half period of the external field is approximately equal to the metastable lifetime of the system. We employ finite-size scaling analysis to investigate the characteristics of this dynamical phase transition. The critical exponents and the fixed-point value of the fourth-order cumulant are found to be consistent with the universality class of the two-dimensional equilibrium Ising model. This universality class has previously been established for the same nonequilibrium model evolving under the standard Glauber dynamic, as well as in a different nonequilibrium model of CO oxidation. The results reported in the present paper support the hypothesis that this far-from-equilibrium phase transition is universal with respect to the choice of the stochastic dynamics.