Roaming Dynamics in Hydroxymethyl Hydroperoxide Decomposition Revealed by the Full-Dimensional Potential Energy...

The CH₂OO + H₂O reaction is an important atmospheric process that leads to the formation of formic acid (HCOOH) and water via the intermediate hydroxymethyl hydroperoxide (HOCH₂OOH, HMHP). We investigated the intricacies of this process by employing quasiclassical trajectory calculations on an accurate, full-dimensional ab initio potential energy surface (PES). In addition to the direct mechanism via the transition state (TS), an interesting roaming mechanism was found to play the predominant role in producing H₂O and HCOOH. This roaming pathway is featured as the near direct dissociation of HMHP into OH and hydroxymethoxy radical, followed by the retraction of OH and abstraction of the H atom, culminating in the formation of H₂O. Due to the longer interaction time of the roaming mechanism, less product translational energy was released, but more internal energies of HCOOH were obtained, as compared with the direct TS mechanism. The enhanced yield of H₂O and formic acid achieved through roaming dynamics underscores the significance of dynamics simulations based on an accurate full-dimensional PES. This work provides new insights into the dynamics of the CH₂OO + H₂O reaction and its implications for atmospheric chemistry.