Auto-construction of complex reaction networks in heterogeneous catalysis

In this work, we propose an approach for the auto-construction of complex reaction networks in heterogeneous catalysis. In particular, we employ ab initio replica exchange molecular dynamics (MD) to sample the chemical space, followed by a Markov state model built from the MD trajectories to construct the reaction networks without prior knowledge about the energy landscape. Finally, the transition path theory (TPT) method is then employed to calculate the transition rates of different transition pathways in the reaction network. As a result, the contributions of different stable and meta-stable configurations of the catalysts to the reaction can be quantified at finite temperatures. This approach is illustrated in a model reaction, the O₂ activation on Ag₄ clusters.