Separability of tight and roaming pathways to molecular decomposition.

摘要: Recent studies have questioned the separability of tight and roaming mechanisms to molecular decomposition. We explore this issue for a variety reactions including MgH(2) → Mg + H(2), NCN CNN, H(2)CO H(2) CO, CH(3)CHO CH(4) HNNOH N(2) H(2)O. Our analysis focuses on role second-order saddle points in defining global dividing surfaces that encompass both first-order points. The define an energetic criterion two mechanisms. Furthermore, plots differential contribution reactive flux along paths connecting first- provide dynamic separability. minimum neighborhood point plays mechanism divider, with presence strong indicating are dynamically distinct. show divider is often, but not always, associated point. For formaldehyde acetaldehyde reactions, we find energy geometry conical intersection processes. HNNOH, again processes separable no intrinsic feature potential surface divider. Overall, our calculations suggest generally over broad ranges covering most kinetically relevant regimes.