Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “bond angles”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Structural and electronic properties of rare-earth chromites: A computational and experimental study

Here, in this work, the structural, optical, and electronic properties of rare-earth perovskites of the general formula R⁢ CrO 3 , where R⁢ represents the rare-earth Gd, Tb, Dy, Ho, Er, and Tm, have been studied in detail. These compounds were synthesized through a facile citrate route. X-ray diffraction, Raman spectroscopy, and UV-Visible spectroscopy were utilized to reveal the structural evolutions in R⁢ ⁢CrO 3 . The lattice parameters, Cr 3+ –O 2 –Cr 3+ bond angle, and CrO 6 octahedral distortions were found to strongly depend on the ionic radii of R⁢ . First-principles calculations based on density-functional theory within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) and strongly constrained and appropriately normed (SCAN) meta-GGA were also employed to calculate the structural and electronic properties of R⁢ ⁢CrO 3 . The ground-state energy, lattice constants, electronic structures, and density of states of R⁢ ⁢CrO 3 were calculated. These provide some insights into the electronic characteristics of the R⁢ ⁢CrO 3 compounds. The calculated values of lattice parameters and band gaps with Hubbard U correction (SCAN+ U ) agree well with values measured experimentally and show more accuracy in predicting the ground-state crystal structure and band structure compared to PBE+ U approximation. The band gap of R⁢ ⁢CrO 3 is found to be independent of the ionic radii of R⁢ from both experiments and calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Manipulating Spin–Lattice Coupling in Layered Magnetic Topological Insulator Heterostructure via Interface Engineering

Induced magnetic order in a topological insulator (TI) can be realized either by depositing magnetic adatoms on the surface of a TI or engineering the interface with epitaxial thin film or stacked assembly of 2D van der Waals (vdW) materials. Herein, the observation of spin-phonon coupling in the otherwise non-magnetic TI Bi 2 Te 3 is reported, due to the proximity of FePS 3 (an antiferromagnet (AFM), T N ≈ 120 K), in a vdW heterostructure framework. Temperature-dependent Raman spectroscopic studies reveal deviation from the usual phonon anharmonicity originated from spin-lattice coupling at the Bi 2 Te 3 /FePS 3 interface at/below 60 K in the peak position (self-energy) and linewidth (lifetime) of the characteristic phonon modes of Bi 2 Te 3 (106 and 138 cm –1 ) in the stacked heterostructure. The Ginzburg-Landau (GL) formalism, where the respective phonon frequencies of Bi 2 Te 3 couple to phonons of similar frequencies of FePS 3 in the AFM phase, is adopted to understand the origin of the hybrid magneto-elastic modes. At the same time, the reduction of characteristic TN of FePS 3 from 120 K in isolated flakes to 65 K in the heterostructure, possibly due to the interfacial strain, which leads to smaller Fe-S-Fe bond angles as corroborated by computational studies using density functional theory (DFT). Besides, inserting hexagonal boron nitride within Bi 2 Te 3 /FePS 3 stacking regains the anharmonicity in Bi 2 Te 3 . As a result, controlling interfacial spin-phonon coupling in stacked heterostructure can have potential application in surface code spin logic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

On the Emergence of Ferromagnetism in LaCoO 3 Ultrathin Films

It is well known that the properties of a crystal evolve as it increases in size from a single atomic plane to that of the bulk. Such size-dependent transitions can stem from many different origins and depend on minute changes to crystal bonding and composition. Here, a model example is that of LaCoO 3 , which is non-magnetic in the bulk but can display ferromagnetism at the nanoscale. Here, the evolution of structure-property relationships is studied in the LaCoO 3-δ /SrTiO 3 (001) system as the thickness of LaCoO 3-δ is increased from a single plane to 10 unit cells. In situ synchrotron X-ray studies are performed during and post-deposition to probe changes in the interactions between structure, stoichiometry, and magnetic behavior. Structural quantification indicates that the oxygen octahedral rotation pattern evolves with thickness, due to inherent differences in crystal symmetry between the film and substrate. The change in rotation modifies the required energy barrier for the spin state transition via the Co–O bond length and Co–O–Co bond angle, affecting the appearance of ferromagnetism. Our results highlight the contributions of high spin Co 2+ and/or high spin Co 3+ to respective weak and robust ferromagnetism and the evolution of properties with size in ultrathin LaCoO 3-δ heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Pressure‐Dependent “Insulator–Metal–Insulator” Behavior in Sr‐Doped La 3 Ni 2 O 7

Abstract Recently, superconductivity at high temperatures is observed in bulk La 3 Ni 2 O 7−δ under high pressure. However, the attainment of high‐purity La 3 Ni 2 O 7−δ single crystals remains a formidable challenge. Here, the crystal structure and physical properties of single crystals of Sr‐doped La 3 Ni 2 O 7 synthesized at high pressure (20 GPa) and high temperature (1400 °C) are reported. Through single crystal X‐ray diffraction, it is shown that high‐pressure‐synthesized paramagnetic Sr‐doped La 3 Ni 2 O 7 crystallizes in an orthorhombic structure with Ni─O─Ni bond angles of 173.4(2)° out‐of‐plane and 175.0(2)°and 176.7(2)°in plane. The substitution of Sr alters in band filling and the ratio of Ni 2+ /Ni 3+ in Sr‐doped La 3 Ni 2 O 7 , aligning them with those of “La 3 Ni 2 O 7.05” , thereby leading to significant modifications in properties under high pressure relative to the unsubstituted parent phase. At ambient pressure, Sr‐doped La 3 Ni 2 O 7 exhibits insulating properties, and the conductivity increases as pressure goes up to 10 GPa. However, upon further increasing pressure beyond 10.7 GPa, Sr‐doped La 3 Ni 2 O 7 transits back from a metal‐like behavior to an insulator. The insulator–metal–insulator trend under high pressure dramatically differs from the behavior of the parent compound La 3 Ni 2 O 7−δ , despite their similar behavior in the low‐pressure regime. These experimental results underscore the considerable challenge in achieving superconductivity in nickelates.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evolution of the Electronic and Excitonic Properties in 2D Ruddlesden–Popper Perovskites Induced by Bifunctional Ligands

2D Ruddlesden–Popper metal‐halide perovskites exhibit structural diversity due to a variety of choices of organic ligands. Incorporating bifunctional ligands in such materials is particularly intriguing since it can result in novel electronic properties and functions. However, an in‐depth understanding of the effects of bifunctional ligands on perovskite structures and, consequently, their electronic and excitonic properties, is still lacking. Here, in this work, n = 1 2D perovskites built with organic ligands containing ─CN, ─OH, ─COOH, ─phenyl (Ph), and ─CH 3 functional groups are investigated using ultraviolet and inverse photoemission spectroscopies, density functional theory calculations, and tight‐binding model analyses. The experimentally determined electronic gaps of the ─CN, ─COOH, ─Ph, and ─CH 3 based perovskites exhibit a strong correlation with the in‐plane Pb─I─Pb bond angle, while the ─OH based perovskite deviates from the linear trend. Based on the band structure calculations, this anomaly is attributed to the out‐of‐plane dispersion, caused predominantly by significant interlayer electronic coupling that is present in ─OH based perovskites. These results highlight the complex and diverse impacts of organic ligands on electronic properties, especially in terms of the involvement of strong interlayer electronic coupling. The impact of the bifunctional ligands on the evolution of the exciton binding energy is also addressed.

2D perovskites↗
DOE OSTI2025

Influence of isoelectronic mass modulation on phonon decay and transport in layered pnictogen-carbon systems

This study systematically investigates the structural, electronic, and thermal transport properties of layered pnictogen–carbon (Pn 2 C 2 ; Pn = P, As, Sb, Bi) monolayers, revealing a profound influence of isoelectronic mass modulation on phonon dynamics and thermal conductivity. Through first-principles calculations and lattice dynamics analysis, we demonstrate that increasing the atomic mass of pnictogens leads to elongated Pn-C bonds, weakened interatomic interactions, and enhanced phonon-phonon scattering, resulting in a dramatic reduction in lattice thermal conductivity (κ). Specifically, κ decreases exponentially from 65.6 W/m-K in P 2 C 2 to an ultralow 0.37 W/m-K in Bi 2 C 2 , driven by suppressed acoustic-optical phonon gaps Δ$^{Γ}_{A-0}$, increased anharmonicity, and reduced phonon lifetimes and group velocities. The transition from semiconducting to metallic behavior in heavier pnictogen-based systems further enhances phonon-electron scattering, contributing to thermal conductivity suppression. Structural analysis highlights the strengthening of out-of-plane C—C bonds and the contraction of C—Pn—C bond angles, which disrupt in-plane phonon transport. Further, these findings establish a design framework for engineering ultralow-κ materials through chemical substitution and structural tuning, offering significant potential for thermoelectric and thermal management applications. This work provides fundamental insights into phonon decay mechanisms and thermal transport in 2D materials, paving the way for advanced phononic and energy-efficient devices.

2D materials↗
DOE OSTI2022

Determination of the structure of lithium niobosilicate glasses by molecular dynamics simulation with a new Nb-O potential

A partial charge empirical potential for the Nb-O pair has been developed based on existing parameters of other pairs in a Teter potential to enable molecular dynamics simulations of both lithium niobate crystal and lithium niobosilicate glasses. The developed potential is capable of describing structural features of lithium niobosilicate glasses in a wide composition range, including niobium coordination number and bond length, density, bond angle distribution, polyhedral distribution and fraction of bridging oxygen. Furthermore, the results obtained using this new potential show good agreement with experimental data of density and structure from Raman spectroscopy of lithium niobosilicate glasses and X-ray absorption spectroscopy near Nb K-edge.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Depicting the roles of CuO secondary phase and heat treatment in driving the magnetic and magnetocaloric features of Pr 2/3 Sr 1/3 MnO 3 manganite

In this work, we report a detailed experimental study regarding the impact of copper oxide (CuO) secondary phase and heat treatments on the structural, magnetic, and magnetocaloric properties of the near-room temperature Pr 2/3 Sr 1/3 MnO 3 (PSMO) magnetic refrigerant. Our investigations are carried out by using structural and microstructural analyses, alongside magnetization measurements. Here, the analysis of X-ray diffraction data of PSMO(95%)-CuO(5%) (PSMO-CuO) samples shows the coexistence of both CuO and PSMO phases. Further, the microstructural analysis of PSMO-CuO reveals that the addition of CuO significantly enhances the grains size. On the other hand, the added secondary phase markedly reduces the Curie temperature (T c ) from 293 K for PSMO to about 273 K for PSMO-CuO composite while increasing the magnetocaloric effect. This decrease in T c is associated with a significant change from 162° to about 156° in the Mn-OII-Mn bond angle respectively. Moreover, performed investigations regarding the role of heat treatments unveil that the observed changes in the structural and magnetic features are mainly driven by the secondary phase that modify grains size and double-exchange interactions in the PSMO compound. Interestingly, our findings demonstrate that the Curie temperature of the PSMO and accordingly its magnetocaloric effect can be tailored by adding small amounts of CuO without need to substitution on cation sites. In the light of obtained results, a multilayered refrigerant composed of PSMO and PSMO-CuO is proposed to cover the magnetic cooling temperature range close to room-temperature. The resulting entropy change remains practically constant between 273 K and 293 K. Such a behavior is highly appreciated from a practical point of view, particularly in cases where the cooling process is carried out by using the AMR and Ericsson cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Local atomic configurations in mechanically alloyed amorphous (FeCoNi) 70 Ti 10 B 20 powders

Here, the atomic structure of amorphous (FeCoNi) 70 Ti 10 B 20 alloy synthesized by mechanical alloying was investigated using high energy synchrotron X-ray diffraction and inverse Monte Carlo simulations of pair distribution functions. Empirical potential structure refinement indicates a chemical short-range order at the length scales of 2.1–2.5 Å via local atomic arrangements forming deformed bcc-like clusters. The structural model obtained was described by bond lengths, coordination numbers, and bond angle distribution functions determined for the first neighbor atoms by x-ray scattering supplemented with 3D Monte Carlo simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A comparative study of the effectiveness of empirical potentials for molecular dynamics simulations of borosilicate glasses

Despite their practical importance, atomistic modeling of B 2 O 3 containing glasses have been challenging due to the lack of reliable empirical potentials. Fortunately, a few recent developments have shown promises to simulate these glasses where the boron coordination has complex and non-linear dependence on glass composition. This work aims to provide an evaluation of the effectiveness of three recently developed potentials by a systematic study of a series (~20) of sodium borosilicate glasses with constant K (ratio of [SiO 2 ]/[B 2 O 3 ]) =2 and varying R (ratio of [Na 2 O]/[B 2 O 3 ] ranging from 0.1 to 4) values and several sodium boroaluminosilicate glasses. A comparative assessment was established on the basis of the short- and medium-range structure features, such as boron N 4 values, total correlation functions, bond angle distribution, oxygen speciation, and mechanical properties using experimental or well-established models as criteria. Furthermore, this work provides insights on the choices of empirical potentials for MD simulations of borosilicate glasses and gives directions of future potential development and refining.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Study of beyond nearest-neighbor environment and intermediate-range order in a sodium aluminosilicate geopolymer using Reverse Monte Carlo modeling

A large scale three-dimensional structural model of a geopolymer with an approximate composition of NaAlSi 2 O 6 .5.5H 2 O obtained by Reverse Monte Carlo (RMC) modeling based on experimental high-energy x-ray diffraction is presented for the first time in order to obtain information regarding beyond nearest-neighbor environment and intermediate-range order (IRO). RMC model exhibits a three-dimensional network consisting of randomly cross-linked AlO 4 and SiO 4 tetrahedral units with uniformly distributed Na atoms and H 2 O molecules. The bond angle distributions, i.e. T-O-T, O-T-O and Na-O-Na angles, are somewhat distorted with lower values compared to analogous crystal systems. The origin of the first peak in the structure factor indicating IRO is investigated using the partial structure factors; Na-Na, Si-Na, Al-Si, O-H, and H-H atom pairs are found to be the main contributors. Ring size distribution analysis demonstrates that the structure mainly involves 6-, 7- and 8-membered rings. Finally, the coherence length of these IRO characteristics is ~10.3 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pressure-driven density match nucleates metastable r8 phases from amorphous Si and Ge

The pressure–temperature phase behavior of covalent disordered solids such as amorphous silicon and germanium is complex. Questions remain on possible glass transitions, on polyamorphism via amorphous–amorphous transitions, on connections with liquid–liquid transitions, on structure-behavior relationships, and on their potential as precursor for novel methods for material discovery. Here we demonstrate experimentally the nucleation of a metastable, four-fold coordinated rhombohedral r8 phase from pure amorphous silicon and germanium upon room temperature compression at pressures below 10 GPa. Accompanying theory reveals a strong pressure-driven distortion of the bond angle transforming the starting tetrahedral low-density amorphous network to a distorted four-fold coordinated medium-density state. This state is of lower density than metallic high-density networks, resembles the crystalline r8 phase and initiates its nucleation. Our finding shows that polyamorphism is not the only possible transformation mode for these amorphous solids and that instead nucleation of interesting functional phases at potentially useful pressures is possible. Such novel access modes to metastable structures are critical for future exploitability and could be useful for other tetrahedral materials including carbon, where the related (bc8) post-diamond phase remains elusive. Our observed density match between an amorphous and a metastable crystalline phase clearly allows for a new phase transition pathway, while corresponding theory demonstrates how carefully validated atomistic simulations can guide prediction, discovery and synthesis of novel material structures.

Materials discovery↗
DOE OSTI2021

Influence of Al location on formation of silver clusters in mordenite

Formation of zeolite supported Ag 0 clusters depends on a combination of thermodynamically stable atomic configurations, charge balance considerations, and mobility of species on the surface and within pores. Periodic density functional theory (DFT) calculations were performed to evaluate how the location of Al in the mordenite (MOR) framework and humidity control Ag 0 nanocluster formation. Four Al framework sites were studied (T1-T4) and the Al positions in the framework were identified by the shifts in the differential Al…Al pair distribution function (PDF). Furthermore, structural information about the Ag 0 nanoclusters, such as dangling bonds, can be identified by Ag…Ag PDF data. For Ag 0 formation in vacuum MOR structures with a Si:Al ratio of 5:1 with Al in the T1 position resulted in the most framework flexibility and the lowest Ag 0 nanocluster charge, indicating the best result for formation of charge neutral nanoclusters. When water is present, Al in the T3 and T4 positions results in the formation of the smallest average Ag 0 nanoclusters plus greater expansion of the O-T-O bond angle than in vacuum, indicating easier diffusion of the Ag 0 nanoclusters to the surface. Here, the presence of Al in 4-membered rings and in pairs indicates favorable MOR structures for formation of single Ag atoms, despite the existence of synthesis challenges. Therefore, Al in the T2 position is the least favorable for Ag 0 nanocluster formation in both vacuum and in the presence of water. Al in the T1, T3, and T4 positions provides beneficial effects through framework flexibility and changes in nanocluster size or charge that can be leveraged for design of zeolites for formation of metallic nanoclusters.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Role of spin-orbit coupling on crystal-field splitting and phase-stability of rare-earth based layered intermetallic

Layered and incommensurate heterostructures have attracted much attention for the occurrence of superconductivity and charge density waves with the possibility of intercalating foreign atoms. However, lanthanide-based heterostructures where (Eu x Sm 1-x )S and TaS 2 are alternatively stacked have been scarcely investigated. In this work, we performed phase stability, bonding behavior and electronic-structure analysis of (Eu x Sm 1-x )TaS 3 using first-principles density-functional theory methods. Our phase stability analysis suggests 50 at.% solubility of Eu in (Eu x Sm 1-x )TaS 3 compared to Eu solubility in all proportions in cubic SmS. The instability of Eu beyond 50 at.% in (Eu x Sm 1-x )TaS 3 was attributed to higher density of Eu-4f states at the Fermi-level. Based on band position calculated from spin-orbit coupling effect, we constructed a qualitative schematic of possible crystal-field analysis. The local change in bond-length and bond-angle around Eu-S in (Eu x Sm 1-x )TaS 3 correlate well with our crystal-field analysis. We believe that quantum mechanical insights provided in this work will be useful to understand other complex heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Determining the Oxygen Stoichiometry of Cobaltite Thin Films

Transition metal oxides (TMO) are promising materials to realize low-power neuromorphic devices. Their physical properties critically depend on their oxygen vacancy concentrations, whose experimental determination remains a challenging task. Here we focus on cobaltites, in particular La 1-x Sr x CoO 3-d (LSCO), and we present a strategy to identify fingerprints of oxygen vacancies in X-ray absorption (XA) spectra. Using a combination of experiment and theory, we show that the variation of the oxygen vacancy concentration in the perovskite phase of LSCO is correlated with the change of the relative peak positions of the O K-edge XA spectra. Furthermore, we also identify an additional geometrical fingerprint that captures both the changes of the Co-O bond length and Co-O-Co bond angle in the material due to the presence of oxygen vacancies. Finally, we predict the oxygen vacancy concentration of experimental samples and show how the resistivity of the oxide material may be tuned as a function of the defect concentration present in the system.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Pressure-Induced Reduction of Dicyanamide by Samarium(II) in a Coordination Polymer

A samarium(II) coordination polymer, [Sm(2.2.2- cryptand)(dca)]I (dca− = dicyanamide), has been prepared from the reaction of SmI2 with tetrabutylammonium dicyanamide and 2.2.2- cryptand. The structure consists of [Sm(2.2.2-cryptand)] 2+ cations bridged by dicyanamide to form corrugated 1D chains. Single crystals of this compound have been studied spectroscopically using UV−vis−NIR and Raman spectroscopy as a function of pressure to reveal a pressureinduced two-electron reduction of dicyanamide by Sm 2+ to cyanide and cyanamide and Sm 3+ between 5 and 8 GPa. High-pressure single-crystal diffraction studies reveal a phase change at 2.6 ± 0.1 GPa, where a polymorph exhibiting a smaller Sm 2+ ···N C bond angle and shorter Sm 2+ ···C distance was observed. These observations provide mechanistic insight into the reduction of dicyanamide into cyanide and cyanamide by pressurized samarium(II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗