Structure of As2Se3 and AsSe network glasses: Evidence for coordination defects and homopolar bonding

The structural properties of As2Se3 and AsSe4 glasses are investigated using the First Principles Molecular Dynamics. The results show an excellent agreement with measured structural properties in real and reciprocal space (total structure factors and total pair distribution functions, differential pair correlation functions). The analysis of the detail of the structure shows that homopolar AsAs not only exist in the stochiometric compound but also for chalcogen rich compositions. Furthermore, coordination defects consisting of four-fold As and 1-fold Se are found to be of about 5–9%. Their topological nature, their evolution with temperature, as well as their contribution to the understanding of floppy to rigid transitions are discussed.

► We investigate As2Se3 and AsSe4 from using the First Principles Molecular Dynamics.
► An excellent agreement with experiments is obtained.
► Details of the structure reveals the presence of homopolar AsAs bonds and coordination defects.
► Their contribution to the flexible/rigid transition is discussed.