Non-IRC Mechanism of Bimolecular Reactions with Submerged Barriers: A Case Study of Si⁺ + H₂O Reaction

Abstract

Chemical reactions with submerged barriers may feature interesting dynamic behaviors that are distinct from those with substantial barriers or those entirely dominated by capture. The Si + + H 2 O reaction is a prototypical example, involving even two submerged saddle points along the reaction path: one for the direct dissociation of H (H-dissociation SP) and another for H migration from the O-side to the Si-side (H-migration SP). We investigated the intricacies of this process by employing quasiclassical trajectory calculations on an accurate, full-dimensional ab initio potential energy surface. Through careful trajectory analysis, an interesting nonintrinsic reaction coordinate mechanism was found to play an important role in producing SiOH + and H. This new pathway is featured as that the H atoms do not form HSiOH + complexes along the minimum-energy path but directly dissociate into the products after passing through the H-migration SP. Furthermore, based on artificially scaled potential energy surfaces (PESs), the impact of barrier height on the reaction is also explored. This work provides new insights into the dynamics of the Si + + H 2 O reaction and enriches our understanding of reactions with submerged barriers.