S- and Se-based chalcogenide glasses are intrinsically metastable and exhibit a number of photo-induced effects unique to this class of materials, reversible photostructural changes and photo-induced anisotropy being major examples. These effects are usually interpreted in terms of the formation of valence alternation pairs and 'wrong' bonds. In this work, using density functional theory simulations, we demonstrate for the case example of As2S3 that a strong decrease in the optical band gap can be achieved if a polymorphic transformation of the local structure from orpiment to that of tetradymite takes place. For the formation of the latter, the presence of lone-pair electrons in near-linear atomic configurations is crucial. Our results represent a novel approach to understanding the photo-induced structural changes in chalcogenide glasses as being due to the presence of polymorphism, and will lead to their wider use in various photonic devices.
Keywords: chalcogenide glasses; density functional theory; photostructural changes; polymorphism.