Complex Reaction Network Thermodynamic and Kinetic Autoconstruction Based onAb InitioStatistical Mechanics: A Case Study of O₂Activation on Ag₄Clusters

An approach based onab initiostatistical mechanics is demonstrated for autoconstructing complex reaction networks.Ab initiomolecular dynamics combined with Markov state models are employed to study relevant transitions and corresponding thermodynamic and kinetic properties of a reaction. To explore the capability and flexibility of this approach, we present a study of oxygen activation on Ag₄as a model reaction. Specifically, with the same sampled trajectories, it is possible to study the structural effects and the reaction rate of the cited reaction. The results show that this approach is suitable for automatized construction of reaction networks, especially for non-well-studied reactions, which can benefit from thisab initiomolecular dynamics based approach to construct comprehensive reaction networks with Markov state models without prior knowledge about the potential energy landscape.