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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 AsSe by Materials Project

AsSe is BCT5-like structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four AsSe clusters. there are four inequivalent As2+ sites. In the first As2+ site, As2+ is bonded in an L-shaped geometry to two Se2- atoms. Both As–Se bond lengths are 2.41 Å. In the second As2+ site, As2+ is bonded in an L-shaped geometry to two Se2- atoms. Both As–Se bond lengths are 2.41 Å. In the third As2+ site, As2+ is bonded in an L-shaped geometry to two Se2- atoms. Both As–Se bond lengths are 2.41 Å. In the fourth As2+ site, As2+ is bonded in an L-shaped geometry to two Se2- atoms. Both As–Se bond lengths are 2.40 Å. There are four inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a water-like geometry to two As2+ atoms. In the second Se2- site, Se2- is bonded in a water-like geometry to two As2+ atoms. In the third Se2- site, Se2- is bonded in a water-like geometry to two As2+ atoms. In the fourth Se2- site, Se2- is bonded in a water-like geometry to two As2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on As2Se3 by Materials Project

As2Se3 crystallizes in the monoclinic P2_1/c space group. The structure is two-dimensional and consists of two As2Se3 sheets oriented in the (0, 1, 0) direction. there are two inequivalent As3+ sites. In the first As3+ site, As3+ is bonded in a distorted trigonal non-coplanar geometry to three Se2- atoms. There are a spread of As–Se bond distances ranging from 2.43–2.47 Å. In the second As3+ site, As3+ is bonded in a distorted trigonal non-coplanar geometry to three Se2- atoms. There are one shorter (2.42 Å) and two longer (2.47 Å) As–Se bond lengths. There are three inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a water-like geometry to two As3+ atoms. In the second Se2- site, Se2- is bonded in a water-like geometry to two As3+ atoms. In the third Se2- site, Se2- is bonded in an L-shaped geometry to two As3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on As2Se3 by Materials Project

As2Se3 crystallizes in the monoclinic C2/m space group. The structure is two-dimensional and consists of two As2Se3 sheets oriented in the (1, 0, 0) direction. there are two inequivalent As3+ sites. In the first As3+ site, As3+ is bonded to six Se2- atoms to form edge-sharing AsSe6 octahedra. There are a spread of As–Se bond distances ranging from 2.58–2.85 Å. In the second As3+ site, As3+ is bonded in a 5-coordinate geometry to five Se2- atoms. There are a spread of As–Se bond distances ranging from 2.45–3.19 Å. There are three inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a 3-coordinate geometry to three As3+ atoms. In the second Se2- site, Se2- is bonded in a 5-coordinate geometry to five As3+ atoms. In the third Se2- site, Se2- is bonded in a 3-coordinate geometry to three equivalent As3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on As2Se by Materials Project

As2Se crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. As1+ is bonded in a linear geometry to two equivalent Se2- atoms. Both As–Se bond lengths are 2.66 Å. Se2- is bonded in a 4-coordinate geometry to four equivalent As1+ atoms.

36 MATERIALS SCIENCE↗