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Abstract: The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide, C u 1 / 3 A g 1 / 3 A u 1 / 3 CN , with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN, and bimetallic cyanides M x M ′ 1 − x CN ( M , M ′ = Cu , Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them. C u 1 / 3 A g 1 / 3 A u 1 / 3 CN exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function analysis and 13 C solid-state nuclear-magnetic-resonance measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However, NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in C u 1 / 3 A g 1 / 3 A u 1 / 3 CN , the metals in neighboring chains cannot all be truly coplanar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature.

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Abstract: We present new results on solid (monolithic) synthetic C-S-H made at room temperature from easily obtainable calcium sources (calcium oxide, calcium hydroxide) and nanosilica (w/s = 2) with a 2 minute mixing time. Using synchrotron X-ray diffraction combined with TGA/DSC, 29Si NMR and synchrotron pair distribution function (PDF) data we show that the solid C-S-H is crystallographically similar to the more conventionally made synthetic C-S-H slurry. We show that C-S-H is present after 1 day curing (C/S = 0.81) and no X-ray visible portlandite is present at day 3. PDF data shows that the ordered domain size is 2.5 – 4.5 nm, depending on the fit chosen.

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Abstract: Four types of magic-size CdS clusters and three different CdS quantum dots have been studied using the technique of X-ray total scattering and pair distribution function analysis. We found that the CdS quantum dots could be modelled as a mixed phase of atomic structures based on the two bulk crystalline phases, which is interpreted as representing the effects of random stacking of layers. However, the results for the magic-size clusters are significantly different. On one hand, the short-range features in the pair distribution function reflect the bulk, indicating that these structures are based on the same tetrahedral coordination found in the bulk phases (and therefore excluding new types of structures such as cage-like arrangements of atoms). But on the other hand, the longer-range atomic structure clearly does not reflect the layer structures found in the bulk and the quantum dots. We compare the effect of two ligands, phenylacetic acid and oleic acid, showing that in one case the ligand has little effect on the atomic structure of the magic-size nanocluster, and in another it has a significant effect.

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Abstract: Non-graphitic carbons (NGCs) represent the most abundant class of \(sp^2\)-hybridized carbon materials (coal, char coal, activated carbon, etc.). These carbons consist of small graphene layer stacks possessing significant structural disorder both in the single graphene sheets and the stacking. In this study an advanced evaluation approach for the wide-angle neutron scattering (WANS) was developed, based on the method introduced by Ruland and Smarsly (2002). In particular, we elucidated if and how the enhanced WANS data quality and larger values of the modulus of the scattering vector \(s\)-range affect the accuracy and the values of the size and disorder parameters - being fitting parameters by themselves - in comparison to wide-angle x-ray scattering (WAXS), which is usually performed by laboratory equipment. We find a reasonable agreement for the parameters \(L_\mathrm{a}\) and \(L_\mathrm{c}\), i.e. the lateral dimension and stack height, within the error bars, while for the disorder parameters different results for WAXS and WANS were found, the origin of which is discussed. Thus, this study addresses the general issue of how reliably microstructural parameters can be determined from WAXS/WANS, by fitting simulated WAXS and WANS curves, which are quality-impaired by added Gaussion noise at different levels and cut-off at different \(s\)-values. From this analysis we estimated the minimal data quality required for a reliable NGC microstructural analysis based on WAXS/WANS. As an important finding, these simulations show that typical, standard WAXS laboratory setups are sufficient to provide reliable values for the most relevant structural parameters. Furthermore, pair-distribution function (PDF) analyses were performed on WAXS data obtained from a Synchrotron facility. Comparing PDF and WAXS/WANS fitting analysis thus suggests the presence of small highly ordered oligoaromatic domains embedded in the larger graphene sheets, questioning the classical view on the NGC microstructure.

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Abstract: Owing to their intrinsically low thermal conductivity and chemical diversity, materials within the I–V–VI2 family, and especially AgBiSe2, have recently attracted interest as promising thermoelectric materials. However, further investigations are needed in order to develop a more fundamental understanding of the origin of the low thermal conductivity in AgBiSe2, to evaluate possible stereochemical activity of the 6s2 lone pair of Bi3+, and to further elaborate on chemical design approaches for influencing the occurring phase transitions. In this work, a combination of temperature-dependent X-ray diffraction, Rietveld refinements of laboratory X-ray diffraction data, and pair distribution function analyses of synchrotron X-ray diffraction data is used to tackle the influence of Sb substitution within AgBi1–xSbxSe2 (0 ⩽ x ⩽ 0.15) on the phase transitions, local distortions, and off-centering of the structure. This work shows that, similar to other lone-pair-containing materials, local off-centering and distortions can be found in AgBiSe2. Furthermore, electronic and thermal transport measurements, in combination with the modeling of point-defect scattering, highlight the importance of structural characterizations toward understanding changes induced by elemental substitutions. This work provides new insights into the structure–transport correlations of the thermoelectric AgBiSe2.