Similar chemical structures, dissimilar triplet quantum yields: a CASPT2 model rationalizing the trend of triplet...

The photophysics of nitroaromatic compounds is characterized by an ultrafast decay into the triplet manifold and by significant triplet quantum yields. The latter quantity changes drastically depending on the system, as shown for 2-nitronaphthalene, 1-nitronaphthalene, and 2-methyl-1-nitronaphthalene, whose triplet quantum yields have been previously measured to be 0.93 ± 0.15, 0.64 ± 0.12, and 0.33 ± 0.05, respectively (J. Phys. Chem. A, 2013, 117, 14100). In this study, we rationalize the reported trend of the triplet quantum yield on the basis of the different abilities of the excited S₁ state to reach a previously unreported conical intersection with the ground state. This path is in competition with the path leading to the triplet state, which appears to be equally favorable in the three systems. The energy barriers from the S₁ CASPT2//CASSCF minima to a CASPT2 minimum-energy-crossing-point of the S₁/S₀ conical intersection have been computed to follow the same trend as the triplet quantum yields of the nitroaromatic systems under analysis. The path has also been characterized for nitrobenzene; an energy barrier was obtained that nicely fits the derived model and is in agreement with its triplet quantum yield value (>0.8). The ability of the present model to not only rationalize the experimental data of a single molecule but also to reproduce a trend for four slightly different systems demonstrates its reliability.