Analysis of the Ability of C₆H₅I to Phosphoresce

The heavy atom effect is a widely utilized strategy to enhance the phosphorescence intensity of organic molecules. Among the preferred choices, heavy halogen atoms such as bromine (Br) or iodine (I) have gained popularity. However, the incorporation of these heavy atoms can introduce challenges due to the presence of unstable excited states that undergo dissociation upon excitation. This study focuses on investigating the excited states of the C₆H₅I molecule, with particular emphasis on the intricate interplay of spin-orbital coupling effects, employing multireference ab initio methodologies. The absence of phosphorescence in the C₆H₅I molecule is attributed to the efficient energy transfer to dissociative excited states and the near-zero spin-orbital coupling between stable triplet sub-levels and the ground singlet state. To gain insights into the explicit dynamics of the excited states, the research employed Ehrenfest dynamics driven by real-time time-dependent density functional theory (TDDFT). Furthermore, the study explored the complete active space compositions and various post-CASSCF (complete active space self-consistent field) approaches.