Impact of Te on the structure and 77Se NMR spectra of Se-rich Ge–Te–Se glasses: a combined experimental and computational investigation†
Selenium-rich Ge–Te–Se glasses have been synthesized along the GeSe4–GeTe4 pseudo-composition line and acquired by 77Se Hahn echo magic-angle spinning NMR. The comparison with the GeSe4 spectrum shows a drastic modification of the typical double-resonance lineshape even at low Te concentrations (<10%). In order to rationalize this feature and to understand the effect of Te on the structure of our glasses, first-principles molecular dynamics simulations and gauge including projector augmented wave NMR parameter calculations have been performed. The distribution of the tellurium atoms in the selenium phase was shown to be mainly responsible for the 77Se lineshape changes. Another possible factor related to the perturbation of the δiso value due to Te proximity appears to be much more limited in the bulk, while the results obtained using molecular models suggest shifts of several hundreds of ppm.