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A review of the application of 2D isotropic-anisotropic correlation NMR spectroscopy in structural studies of chalcogenide glasses

The application of solid-state high-resolution NMR spectroscopy in the structural investigation of chalcogenide glasses in Ge/As/P/Si-X (X = S, Se,Te) systems has remained challenging even for the spin-1/2 nuclides ( 29 Si, 31 P, 77 Se, 125 Te), owing to their low natural abundance (except for 31 P), slow spin-lattice relaxation rate and large CSA and chemical shift distribution induced line broadening effects. However, most of these deleterious effects can be successfully overcome in two-dimensional (2D) isotropic-anisotropic correlation NMR experiments, especially when performed at high magnetic field and in conjunction with the Car-Purcell-Meiboom-Gill (CPMG) echo train acquisition. Here, we present a short introduction to the basic principles of such experiments and review their applications over the last decade in deciphering various short- and intermediate- range structural characteristics of chalcogenide glasses in S-Se, Se-Te, Ge-Se, As-Se and Si-Se systems as well as in investigating the molecular dynamics in a P-Se supercooled liquid. We anticipate possible future applications of these 2D isotropic-anisotropic correlation NMR experiments, particularly in conjunction with density functional theory-based calculations of NMR chemical shift tensor parameters and additional signal enhancement schemes, in addressing complex structural correlations and distributions in chalcogenide glasses.

2D NMR↗

Materials Data on P2Se5 by Materials Project

P2Se5 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four unii-w3nrx99tzk molecules. there are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded in a trigonal non-coplanar geometry to three Se2- atoms. There are a spread of P–Se bond distances ranging from 2.26–2.28 Å. In the second P5+ site, P5+ is bonded in a trigonal non-coplanar geometry to three Se2- atoms. There are two shorter (2.26 Å) and one longer (2.28 Å) P–Se bond lengths. There are five inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a distorted single-bond geometry to one P5+ atom. In the second Se2- site, Se2- is bonded in a distorted single-bond geometry to one P5+ atom. In the third Se2- site, Se2- is bonded in a distorted single-bond geometry to one P5+ atom. In the fourth Se2- site, Se2- is bonded in a distorted single-bond geometry to one P5+ atom. In the fifth Se2- site, Se2- is bonded in an L-shaped geometry to two P5+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on P2Se by Materials Project

PPSe crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. P1+ is bonded in a linear geometry to two equivalent Se2- atoms. Both P–Se bond lengths are 2.52 Å. Se2- is bonded in a 4-coordinate geometry to four equivalent P1+ atoms.

36 MATERIALS SCIENCE↗