Mechanistic Investigations on the Photoisomerization Reactions of Five-Membered Ring Heterocyclic Molecules Containing Sulfur and Selenium Atoms

The restricted active space self-consistent field method in the 26-electron/27-orbital active space and the 6-311­(d) basis set has been used to investigate the mechanisms of the photochemical isomerization reactions concerning the model systems of 1,2,3-thiadiazole and 1,2,3-selenadiazole. The computational works suggest that the preferred reaction paths for both 1,2,3-thiadiazole and 1,2,3-selenadiazole are as follows: reactant → Franck–Condon region → conical intersection → intermediate → transition states → photoproducts. As a result, the structures of the conical intersections, which play a decisive role in these photoisomerization reactions, are obtained. In particular, the present theoretical evidences demonstrate that the potential energy surfaces for the formation of 1,3-diradicals are quite flat. This may explain why their experimental detections are so difficult