A Caching Scheme To Accelerate Kinetic Monte Carlo Simulations of Catalytic Reactions

Kinetic Monte Carlo (KMC) simulations have been instrumental in advancing our fundamental understanding of heterogeneously catalyzed reactions, with particular emphasis on structure sensitivity, ensemble effects, and the interplay between adlayer structure and adsorbate-adsorbate lateral interactions in shaping the observed kinetics. Yet, the computational cost of KMC remains high, thereby motivating the development of acceleration schemes that would improve the simulation efficiency. We present an exact such scheme, which implements a caching algorithm along with shared-memory parallelization to improve the computational performance of simulations incorporating long-range adsorbate-adsorbate lateral interactions. This scheme is based on caching information about the energetic interaction patterns associated with the products of each possible lattice process (adsorption, desorption, reaction etc.). Thus, every time a reaction occurs ("ongoing reaction"), it enables fast updates of the rate constants of "affected reactions", i.e., possible reactions in the region of influence of the "ongoing reaction". Benchmarks on KMC simulations of NO oxidation/reduction, yielded acceleration factors of up to 20, when comparing single-thread runs without caching to runs on 16 threads with caching, for simulations with a cluster expansion Hamiltonian that incorporates up to 8th-nearest-neighbor interactions.