Bonding nature of local structural motifs in amorphous GeTe.

Despite its simple chemical constitution and unparalleled technological importance, the phase-change material germanium telluride (GeTe) still poses fundamental questions. In particular, the bonding mechanisms in amorphous GeTe have remained elusive to date, owing to the lack of suitable bond-analysis tools. Herein, we introduce a bonding indicator for amorphous structures, dubbed "bond-weighted distribution function" (BWDF), and we apply this method to amorphous GeTe. The results underline a peculiar role of homopolar Ge-Ge bonds, which locally stabilize tetrahedral fragments but not the global network. This atom-resolved (i.e., chemical) perspective has implications for the stability of amorphous "zero bits" and thus for the technologically relevant resistance-drift phenomenon.

Influence of the Ba2+/Sr2+ content and oxygen vacancies on the stability of cubic Ba(x)Sr(1-x)Co(0.75)Fe(0.25)O(3-δ).

We present a theoretical and experimental study on the influence of the Ba/Sr and Co/Fe ratios as well as the oxygen-non-stoichiometry on the stability of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). Thin-layer depositions are analysed by looking at TEM images and EDX spectra. Bond-analytical calculations are performed to explain the stability difference between hexagonal and cubic BSCF. Finally, annealing experiments analysed using XRD give an insight into the differences of phase-fraction growth with respect to the Ba/Sr ratio.

Ab initio study of the high-temperature phase transition in crystalline GeO2.

Germanium dioxide (GeO2 ) takes two forms at ambient pressure: a thermodynamically stable rutile-type structure and a high-temperature quartz-type polymorph. Here, we investigate the phase stability at finite temperatures by ab initio phonon and thermochemical computations. We use gradient-corrected density-functional theory (PBE-GGA) and pay particular attention to the modeling of the "semicore" germanium 3d orbitals (ascribing them either to the core or to the valence region). The phase transition is predicted correctly in both cases, and computed heat capacities and entropies are in excellent agreement with thermochemical database values. Nonetheless, the computed formation energies of α-quartz-type GeO2 (and, consequently, the predicted transition temperatures) differ significantly depending on theoretical method. Remarkably, the simpler and cheaper computational approach produces seemingly better results, not worse. In our opinion, GeO2 is a nice test case that illustrates both possibilities and limitations of modern ab initio thermochemistry.

[Co(I)(CN)2(CO)3]-, a new discovery from an 80-year-old reaction.

A systematic study of the 80-year-old simple and fundamental reaction of cobalt(II) salt with cyanide under one atmosphere CO was carried out and two novel Co(I) complexes were isolated in the absence of hydroxide. These complexes are the first structurally characterized mixed cobalt CO-CN(-) compounds.