77Se solid-state NMR of As2Se3, As4Se4 and As4Se3 crystals: a combined experimental and computational study

Abstract

⁷⁷Se NMR parameters for three prototypical crystalline compounds (As₂Se₃, As₄Se₄ and As₄Se₃) have been determined from solid-state NMR spectra in the framework of an investigation concerning As_xSe_(1–x) glass structure understanding. Density functional NMR calculations using the gauge including projector augmented wave methodology have been performed on X-ray and optimized crystal structures for a set of selenium-based crystals. These theoretical results have been combined with the experimental data in order to achieve a precise assignment of the spectral lines. This work and the high sensitivity of solid-state NMR to local order show that the structure of As₄Se₃ should be reinvestigated using state-of-the-art diffraction techniques. Calculations performed on several molecules derived from the crystal structures have demonstrated the limited effect of interlayer or intermolecular interactions on the isotropic chemical shifts. These interactions are therefore not responsible for the unexpected large chemical shift difference observed between these three systems that could mostly be attributed to the presence of short rings.