A novel algorithm is presented that achieves temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate time scales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC were designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the time scales of the slow kinetically relevant nonequilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation, and the reaction rate constants are rescaled accordingly. The algorithm was utilized here to model the CO methanation on stepped metal surfaces. This reaction network has multiple time-scale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to perform quite well; however, we identify a few challenging cases in which the performance is poor. By identifying the underlying cause of these cases of poor performance, we devise possible directions for future algorithm development. Exluding these few challenging cases, the computational savings of the algorithm are found to span many orders of magnitude, and the computational cost should not be limited by the magnitude of the time scale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.

Generalized temporal acceleration scheme for kinetic Monte Carlo simulations of surface catalytic processes by scaling the rates of fast reactions

2019 Spring National Meeting

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