Sulfur, Selenium and Tellurium Ring Clusters: Experimentaland Density-Functional Theoretical Study of Polarized OpticalAbsorption and Raman Spectra, Light-Induced Effects and Conical Intersections

We studied experimentally and computationally the structures and optical properties of sulfur (S), selenium (Se) and tellurium (Te) ring clusters. We encapsulated S, Se and Te into AFI, MOR, CHA and LTA zeolites via vapor adsorption or high-pressure injection from melt and studied Raman and optical absorption spectra (RS and OAS, respectively) of zeolite single crystals with incorporated S, Se and Te ring clusters. Importantly, strict orientation of the rings in zeolite crystals allowed us to study the polarization/orientation dependency of ring RS and OAS. The obtained experimental spectra are found to be in agreement with density functional theory results (DFT using the PBE0 functional and def2-TZVP basis sets) for S8, Se6, Se8, Se12, Te6 and Te8 ring molecules. The agreement is especially good for Te rings, while for S and Se rings harmonic frequency scaling factors are required. The S and Se rings display light-induced effects, which we attribute to the presence of conical intersections between their ground and excited electronic states, resulting in isomerization and subsequent fragmentation. We consider this effect using the Se6 ring example. This phenomenon is important for understanding photostructural changes not only in chalcogen clusters but also in bulk materials such as amorphous selenium.