Segregation model boundary conditions

They found reasonable agreement in the segregation trends predicted by tbeir model and observed in their experiments (Figure 10.1 lb). Comparing results with MD simulations from Hong et al. (2001), these results emphasize the importance of boundary conditions, particularly in determining tbe crossover between density- or mass-dominated segregation effects and size-dominated effects. 

We have studied above a model for the surface reaction A + 5B2 -> 0 on a disordered surface. For the case when the density of active sites S is smaller than the kinetically defined percolation threshold So, a system has no reactive state, the production rate is zero and all sites are covered by A or B particles. This is quite understandable because the active sites form finite clusters which can be completely covered by one-kind species. Due to the natural boundaries of the clusters of active sites and the irreversible character of the studied system (no desorption) the system cannot escape from this case. If one allows desorption of the A particles a reactive state arises, it exists also for the case S > Sq. Here an infinite cluster of active sites exists from which a reactive state of the system can be obtained. If S approaches So from above we observe a smooth change of the values of the phase-transition points which approach each other. At S = So the phase transition points coincide (y 1 = t/2) and no reactive state occurs. This condition defines kinetically the percolation threshold for the present reaction (which is found to be 0.63). The difference with the percolation threshold of Sc = 0.59275 is attributed to the reduced adsorption probability of the B2 particles on percolation clusters compared to the square lattice arising from the two site requirement for adsorption, to balance this effect more compact clusters are needed which means So exceeds Sc. The correlation functions reveal the strong correlations in the reactive state as well as segregation effects. 

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