Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules

摘要: Radiationless transitions between electronic excited states in polyatomic molecules take place through unavoided crossings of the potential energysurfaces with substantial non-adiabatic coupling respective adiabatic states. While extent time these couplings are large enough, can be reasonably well simulated quantum using trajectory surface hopping-like methods. In addition, complex molecular systems may have multiple “trivial” noninteracting cases, described as sharp peaks strongly localized time. Therefore, their modeling is commonly subjected to identification regions close particular instantaneous nuclear configurations for which actually cross each other. Here, we present a novel procedure identify and treat non-interacting so-called Min-Cost algorithm. The method differentiates interacting (simulated by hops), trivial (detected tracking procedure). We discuss its implementation within our recently developed non-adiabaticexcited statemolecular dynamics framework. Fragments two- four-ring linear polyphenylene ethynylene chromophore units at various separations been used representative system test Our results enable us distinguish analyze main features different types radiationless undertakes during internal conversion.