Intramolecular Radiationless Transitions

摘要: In this paper we consider a theory for intramolecular radiationless transitions in an isolated molecule. The Born–Oppenheimer zero‐order excited states are not pure view of configuration interaction between nearly degenerate states, leading to the broadening state, line shape being Lorentzian. optically state can be described terms superposition molecular eigenstates, and resulting wavefunction exhibits exponential nonradiative decay. linewidth lifetime expressed single parameter, that is square energy manifold all vibronic located within one unit around state. validity criteria occurrence unimolecular transition decay molecule derived. Provided density vibrational large enough (i.e., exceeds reciprocal matrix element) expected take place. gross effects structure on relevant parameters discussed.