Trajectory surface hopping molecular dynamics on Chemiluminescence of cyclic peroxides

Abstract

AbstractChemiluminescence (CL) of peroxides is one of the most highly sensitive and most useful analytical techniques. Although the mechanisms of CL were studied experimentally and theoretically in the past decades, the chemiexcitation that a ground‐state specie being excited from its electronic ground state to yield excited‐state products by a chemical reaction is still not completely understood. Direct dynamics simulation on CL reaction which takes into account the full complexity of the relevant potential energy surface characterizes nonadiabatic processes involved in chemiexcitation and could provide access not only to the available reaction channels but also to statistical quantities such as reaction times and quantum yields. In the last decade, the trajectory surface hopping (TSH) molecular dynamics (MD) which is one of the mixed quantum‐classical approaches is hence adopted to simulate the nonadiabatic process in CL of cyclic peroxides. In this article, the basic principle of TSH‐MD and the successful applications on the CL reactions were shortly review.