The molecular structure of hexamethyldigermane determined by gas-phase electron diffraction with theoretical calculations for (CH3)3M-M(CH3)3 Where M = C, Si, and Ge

Gas-phase electron diffraction (GED) data together with results from ab initio molecular orbital calculations (HF and MP2/6-311+G(d,p)) have been used to determine the structure of hexamethyldigermane ((CH3)3Ge-Ge(CH3)3). The equilibrium symmetry is D3d, but the molecule has a very low-frequency, largeamplitude, torsional mode (φCGeGeC) that lowers the thermal average symmetry. The effect of this largeamplitude mode on the interatomic distances was described by a dynamic model which consisted of a set of pseudoconformers spaced at even intervals. The amount of each pseudoconformer was obtained from the ab initio calculations (HF/6-311+G(d,p)). The results for the principal distances (ra) and angles (∠h1) obtained from the combined GED/ab initio (with estimated 1σ uncertainties) are r(Ge-Ge) ) 2.417(2) Å, r(Ge-C) ) 1.956(1) Å, r(C-H) ) 1.097(5) Å, ∠GeGeC ) 110.5(2)°, and ∠GeCH ) 108.8(6)°. Theoretical calculations were performed for the related molecules ((CH3)3Si-Si(CH3)3 and (CH3)3C-C(CH3)3).

A synchrotron powder X-ray diffraction study of the skutterudite-related phases AB1.5Te1.5 (A=Co, Rh, Ir; B= Ge, Sn)

X-ray resonant scattering has been exploited to investigate the crystal structure of the AB1.5Te1.5 phases (A = Co, Rh, Ir; B = Ge, Sn). Analysis of the diffraction data reveals that CoGe1.5Te1.5 and ASn1.5Te1.5 adopt a rhombohedral skutterudite-related structure, containing diamond-shape B2Te2 rings, in which the B and Te atoms are ordered and trans to each other. Anion ordering is however incomplete, and with increasing the size of both cations and anions, the degree of anion ordering decreases. By contrast, the diffraction data of IrGe1.5Te1.5 are consistent with an almost statistical distribution of the anions over the available sites, although some ordered domains may be present. The thermoelectric properties of these materials are discussed in the light of these results.

Oppida, agglomerations and suburbia: the bibracte environs and new perspectives on late Iron Age urbanism in central-eastern France

This paper explores the nature and chronology of La Tène and early Roman unenclosed agglomerations in central-eastern France. It has been prompted by the discovery of a c. 115 ha La Tène D2b/Augustan (c. 50 bc to ad 15) site close to Bibracte in the Morvan, located around the source of the River Yonne. This complex provides a new perspective on the chronology and role of Late La Tène and early Roman unenclosed settlements, adding further complexity to the story of the development of Late La Tène oppida. It indicates that these ‘agglomerations’ followed remarkably varied chronological trajectories, raising important issues concerning the nature of landscape and social change at the end of the Iron Age. Dieser Aufsatz untersucht den Charakter und die Datierung von latènezeitlichen und frührömischen offenen Siedlungen im östlichen Zentralfrankreich. Die Anregung dazu erfolgte durch die Entdeckung einer Latène D2b-zeitlichen bis augusteischen (ca. 50 v. Chr. – 15 n. Chr.) Anlage im Morvan bei Bibracte, die ca. 115 ha Fläche bedeckt und sich um die Quellen des Flusses Yonne erstreckt. Es wird vorgeschlagen, dass dieser Siedlungskomplex eine Ergänzung, aber auch einen Kontrast zu den üblichen Interpretationsmodellen von spätlatènezeitlichen und frührömischen, offenen Großsiedlungen und ihrer zeitlichen Entwicklung darstellt, und weiter zur Komplexität der Entwicklung spätlatènezeitlicher Oppida beiträgt. Es deutet sich an, dass einige der ‘Agglomerationen’ anderen Entwicklungslinien folgen, die wichtige Fragen zur Landschaftsgenese und zum sozialen Wandel am Ende der Eisenzeit aufwerfen. Cet article a pour but d'explorer la nature ainsi que la chronologie des agglomérations ouvertes apparaissant à La Tène Final et au début de la période gallo-romaine du Centre-Est de la France. Il fut inspiré et écrit suite à la découverte dans le Morvan d'un site de 115 ha datant de La Tène D2b et de la période Augustéenne (50 av. J.C. à 15 ap. J.C.) s'étirant autour des Sources de l'Yonne. Cette agglomération apporte de nouvelles perspectives sur la chronologie et sur le rôle des habitats ouverts à la fin de l'Âge du Fer ainsi qu'au début de l'époque gallo-romaine apportant des éléments amenés à renforcer le caractère complexe de l'histoire du développement des oppida à La Tène Final. Cette synthèse tend à démontrer que ces agglomérations suivaient des trajectoires chronologiques variées, élevant un certain nombre de questions, et donc des nouvelles problématiques, concernant la nature du paysage et du changement social à la fin de l'Âge du Fer.