Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Structured”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Preparation of Core-Shell Coordination Molecular Assemblies via the Enrichment of Structure-Directing "Codes" of Bridging Ligands and Metathesis of Metal Units

A series of molybdenum- and copper-based MOPs were synthesized through coordination-driven process of a bridging ligand (3,3'-PDBAD, L-1) and dimetal paddlewheel clusters. Three conformers of the ligand exist with an ideal bridging angle between the two carboxylate groups of 0 degrees (H-2 zeta-L(1)), 120 degrees (H-2 beta-L-1), and of 90 degrees (H-2 beta-L-1), respectively. At ambient or lower temperature, (HL1)-L-2 and Mo-2(OAc)(4) or Cu-2(OAc)(4) were crystallized into a molecular square with ?-L-1 and Mo-2/Cu-2 units. With proper temperature elevation, not only the molecular square with ?-L-1 but also a lantern-shaped cage with a-L-1 formed simultaneously. Similar to how Watson-Crick pairs stabilize the helical structure of duplex DNA, the core-shell molecular assembly possesses favorable H-bonding interaction sites. This is dictated by the ligand conformation in the shell, coding for the formation and providing stabilization of the central lantern shaped core, which was not observed without this complementary interaction. On the basis of the crystallographic implications, a heterobimetallic cage was obtained through a postsynthetic metal ion metathesis, showing different reactivity of coordination bonds in the core and shell. As an innovative synthetic strategy, the site-selective metathesis broadens the structural diversity and properties of coordination assemblies.

Park, J↗
DOE OSTI2014

Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

For LiMO 2 (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li 2 MoO 3 ). A ‘unit cell breathing’ mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in ‘normal’ materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.

Zhou, Yong-Ning↗
DOE OSTI2017

Systematic evaluation of structure–property relationships in heteroacene – diketopyrrolopyrrole molecular donors for organic solar cells

Improved understanding of fundamental structure–property relationships, particularly the effects of molecular shape and intermolecular packing on film morphology and active layer charge transport characteristics, enables more rational synthesis of new p-type small molecules. Here we investigate a series of small molecules consisting of an acene-based electron-rich core flanked by one or two electron-deficient diketopyrrolopyrrole (DPP) moieties. Through minor changes in the molecule structures, measurable variations in the crystal structure and sizable differences in macroscopic properties are achieved. The molecular symmetry as well as the conformation of the side chains affects the unit cell packing density and strength of the intermolecular electronic coupling in single crystals of all molecules in this series. Here, the addition of a second DPP unit to the benzodithiophene (BDT) core increases molecular planarity leading to decreased reorganization energy, strong cofacial coupling, and moderate hole mobility (2.7 × 10 –4 cm 2 V –1 s –1 ). Increasing the length of the acene core from benzodithiophene to naphthodithiophene (NDT) results in a further reduction in reorganization energy and formation of smaller crystalline domains (~11 nm) when mixed with PCBM. Decreasing the aspect ratio of the core using a “zig-zag” naphthodithiophene (zNDT) isomer results in the highest hole mobility of 1.3 × 10 –3 cm 2 V –1 s –1 due in part to tight lamellar (d = 13.5 Å) and π–π stacking (d = 3.9 Å). The hole mobility is directly correlated with the short-circuit current (11.7 mA cm –2 ) and solar cell efficiency (4.4%) of the highest performing zNDT:PCBM device. For each of these small molecules the calculated π-coupling constant is correlated with the hole mobility as a function of crystal structure and orientation indicating the importance of designing molecules that create extended crystalline networks with maximal π-orbital overlap.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Structure and stability of solid Xe(H{sub 2}){sub n}

Mixtures of xenon and molecular hydrogen form a series of hexagonal, van der Waals compounds at high pressures and at 300 K. Synchrotron, x-ray, single crystal diffraction studies reveal that below 7.5 GPa, Xe(H{sub 2}){sub 8} crystallizes in a P3{sup -}m1 structure that displays pressure-induced occupancy changes of two pairs of xenon atoms located on the 2c and 2d sites (while the third pair on yet another 2c site remains fully occupied). The occupancy becomes 1 at the P3{sup -}m1 to R3 transition and all the xenon atoms occupy the 3d sites in the high-pressure structure. These pressure-induced changes in occupancy coincide with volume changes that maintain the average Xe:H{sub 2} stoichiometry fixed at 1:8. The synchrotron x-ray diffraction and Raman measurements show that this unique hydrogen-bearing compound that can be synthesized at 4.2 GPa and 300 K, quenched at low temperatures to atmospheric pressure, and retained up to 90 K on subsequent warming.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The one-loop matter bispectrum in the Effective Field Theory of Large Scale Structures

With this study, given the importance of future large scale structure surveys for delivering new cosmological information, it is crucial to reliably predict their observables. The Effective Field Theory of Large Scale Structures (EFTofLSS) provides a manifestly convergent perturbative scheme to compute the clustering of dark matter in the weakly nonlinear regime in an expansion in k/k NL , where k is the wavenumber of interest and k NL is the wavenumber associated to the nonlinear scale. It has been recently shown that the EFTofLSS matches to 1% level the dark matter power spectrum at redshift zero up to k ≃ 0.3 h Mpc –1 and k ≃ 0.6 h Mpc –1 at one and two loops respectively, using only one counterterm that is fit to data. Similar results have been obtained for the momentum power spectrum at one loop. This is a remarkable improvement with respect to former analytical techniques. Here we study the prediction for the equal-time dark matter bispectrum at one loop. We find that at this order it is sufficient to consider the same counterterm that was measured in the power spectrum. Without any remaining free parameter, and in a cosmology for which kNL is smaller than in the previously considered cases (σ 8 =0.9), we find that the prediction from the EFTofLSS agrees very well with N-body simulations up to k ≃ 0.25 h Mpc –1 , given the accuracy of the measurements, which is of order a few percent at the highest k's of interest. While the fit is very good on average up to k ≃ 0.25 h Mpc –1 , the fit performs slightly worse on equilateral configurations, in agreement with expectations that for a given maximum k, equilateral triangles are the most nonlinear.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Enzyme Design From the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere

Functional, peptide-containing metal complexes with a well-defined peptide structure have the potential to enhance molecular catalysts via an enzyme-like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide-based metal complex built upon the well characterized hydrogen production catalyst, Ni(PPh2NPh)2. The incorporated peptide maintains its B-hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide-based metal complex (~100,000 s-1) is fully retained. The combination of an active molecular catalyst with a structured peptide outer coordination sphere provides a scaffold that permits the incorporation of features of an enzyme-like outer-coordination sphere necessary to create molecular electrocatalysts with en-hanced functionality.

bioinspired↗