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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.

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At least 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Magnetoelastic interactions in SrCu 2 (BO 3 ) 2 studied by Raman scattering experiments and first principles calculations

Dynamic and static crystal lattice properties of SrCu 2 (BO 3 ) 2 are studied by means of Raman scattering, magnetostriction, and thermal expansion measurements in magnetic fields to 45 T. Raman experiments versus temperature reveal that some phonon modes show an unusual behavior: their frequencies soften (modes at 200 and 450 cm –1 ) while others harden (modes at 385 and 478 cm –1 ) when decreasing the temperature below 15 K. Magneto-Raman experiments show that their field dependence correlates with their respective temperature dependencies; e.g., modes that are hardened with increasing temperature also harden with applied magnetic fields and modes that become softer with temperature also soften with applied fields. We use density functional theory to successfully model and compute the energies of these modes, classifying them into two types: pantograph (modes that soften when decreasing the temperature) and nonpantograph. We conclude that the former involves the modification of the intradimer exchange interaction J and the latter the interdimer J'. Lastly, dilatometry is used to correlate field-dependent Raman modes to the closing of the spin gap as well as fractional-magnetization stripe states M = 1/4 M s and M = 1/3 M s , where M s is the saturation magnetization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Tunable MoS{sub 2} bandgap in MoS{sub 2}-graphene heterostructures

Using density functional theory calculations with van der Waals corrections, we investigated how the interlayer orientation affects the structure and electronic properties of MoS{sub 2}-graphene bilayer heterostructures. Changing the orientation of graphene with respect to MoS{sub 2} strongly influences the type and the value of the electronic bandgap in MoS{sub 2}, while not significantly altering the binding energy between the layers or the interlayer spacing. We show that the physical origin of this tunable bandgap arises from variations in the S–S interplanar distance (MoS{sub 2} thickness) with the interlayer orientation, variations which are caused by electron transfer away from the Mo–S bonds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

A hybrid-exchange density functional study of the bonding and electronic structure in bulk CuFeS{sub 2}

The geometric, electronic, and magnetic properties of bulk chalcopyrite CuFeS{sub 2} have been investigated using hybrid-exchange density functional theory calculations. The results are compared with available theoretical and experimental data. The theoretical description of the bonding and electronic structure in CuFeS{sub 2} is analyzed in detail and compared to those computed for chalcocite (CuS{sub 2}) and greigite (Fe{sub 3}S{sub 4}). In particular, the behavior of the 3d electrons of Fe{sup 3+} is discussed in terms of the Hubbard-Anderson model in the strongly correlated regime and found to be similarly described in both materials by an on-site Coulomb repulsion (U) of ∼8.9 eV and a transfer integral (t) of ∼0.3 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Thermal Conductivity of HfTe 5 : A Critical Revisit

Hafnium pentatelluride (HfTe 5 ) has attracted extensive interest due to its exotic electronic, optical, and thermal properties. As a highly anisotropic crystal (layered structure with in-plane chains), it has highly anisotropic electrical-transport properties, but the anisotropy of its thermal-transport properties has not been established. Here, accurate experimental measurements and theoretical calculations are combined to resolve this issue. Time-domain thermoreflectance measurements find a highly anisotropic thermal conductivity, 28:1:8, with values of 11.3 ± 2.2, 0.41 ± 0.04, and 3.2 ± 2.0 W m -1 K -1 along the in-plane a-axis, through-plane b-axis, and in-plane c-axis, respectively. This anisotropy is even larger than what was recently established for ZrTe 5 (12:1:6), but the individual values are somewhat higher, even though Zr has a smaller atomic mass than Hf. Density-functional-theory calculations predict thermal conductivities in good agreement with the experimental data, provide comprehensive insights into the results, and reveal the origin of the apparent anomaly of the relative thermal conductivities of the two pentatellurides. These results establish that HfTe 5 and ZrTe 5 , and by implication their alloys, have highly anisotropic and ultralow through-plane thermal conductivities, which can provide guidance for the design of materials for new directional-heat-management applications and potentially other thermal functionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Unraveling the luminescence signatures of chemical defects in polyethylene

Chemical defects in polyethylene (PE) can deleteriously downgrade its electrical properties and performance. Although these defects usually leave spectroscopic signatures in terms of characteristic luminescence peaks, it is nontrivial to make unambiguous assignments of the peaks to specific defect types. In this work, we go beyond traditional density functional theory calculations to determine intra-defect state transition and charge recombination process derived emission and absorption energies in PE. By calculating the total energy differences of the neutral defect at excited and ground states, the emission energies from intra-defect state transition are obtained, reasonably explaining the photoluminescence peaks in PE. In order to study the luminescence emitted in charge recombination processes, we characterize PE defect levels in terms of thermodynamic and optical charge transition levels that involve total energy calculations of neutral and charged defects. Calculations are performed at several levels of theory including those involving (semi)local and hybrid electron exchange-correlation functionals, and many-body perturbation theory. With these critical elements, the emission energies are computed and further used to clarify and confirm the origins of the observed electroluminescence and thermoluminescence peaks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

First-principles study of the electronic structure and the Fermi surface in rare-earth filled skutterudites R Pt 4 Ge 12

Experiments on rare-earth filled skutterudites demonstrate an intriguing array of thermodynamic, transport, and superconducting properties, and bring to fore theoretical challenges posed by f-electron systems. First-principle calculations based density functional theory and its extensions for strongly correlated systems such as the Hubbard U correction, provide valuable information about electronic structure that can be used to understand experiments. We present a comprehensive study of the electronic structure and Fermi surface of a series of rare-earth filled skutterudites, RPt 4 Ge 12 (where R = La, Ce, Pr), aimed at shedding light on: consequences of progressive increase of f-orbital occupancy in the series; the effects of the Hubbard parameter U; and the Fermi surfaces, band structures, and densities of states. The calculated Fermi surfaces may be relevant to the question of multiband versus single-band superconductivity. Computed densities of states qualitatively explain the available resonant photoemission spectroscopy experiments, and (together with available specific heat measurements) provide estimates of the effective masses. We also show the existence of pseudogaps in the total density of states which may be relevant for the thermoelectric properties of these systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Descriptors for Cu facets for CO2 reduction reaction activity

Computation screening is crucial for designing efficient electrochemical catalysts for carbon dioxide (CO2R) reduction to valuable hydrocarbons and oxygenates. Herein, leveraging density functional theory calculations of the CO adsorption energy ΔE_CO on seventeen Cu terminations, we discover a strong linear correlation between ΔE_CO and the recently experimentally measured CO2R electrochemical currents (ACS Catal. 2022, 12, 11, 6578–6588). Examining the ab initio thermodynamics of the early critical intermediates CO*, COH*, and CHO*, we find that CO* → CHO* is the thermodynamically preferred step, and notably shows a volcano trend with the experimental currents where the maximum CO2R current corresponds to the moderate CHO* formation energy. Importantly, we show that increasing the step and kink density of the Cu termination not only enhances CO adsorption strength but also modulates the CO* → CHO* pathway, as respectively exemplified in the (941) and (741) facets. We also explain why (741) is exceptional with high CO2R activity as measured experimentally due to its relatively low activity toward the hydrogen evolution reaction compared with the other Cu surfaces. Beyond the general CO adsorption energy that only shows a linear trend with CO2R activity, we show that the reaction CO* → CHO* free energy is a descriptor that displays a volcano relationship with the overall CO2R activity on Cu facets.

machine learning↗
DOE OSTI2023

Insights into the Oxygen Evolution Reaction on Graphene-Based Single-Atom Catalysts from First-Principles-Informed Microkinetic Modeling

Single-atom transition metals embedded in nitrogen-doped graphene have emerged as promising electrocatalysts due to their high activity and low material cost. These materials have been shown to catalyze a variety of electrochemical reactions, but their active sites under reaction conditions remain poorly understood. Using first-principles density functional theory calculations, we develop a pH-dependent microkinetic model to evaluate the relative performance of transition metal catalysts embedded in fourfold N-substituted double carbon vacancies in graphene for the oxygen evolution reaction. We find that reaction pathways involving intermediates co-adsorbed on the metal site are preferred on all transition metals. These pathways lead to enhancements in catalytic activity and broaden the activity peak when compared with purely thermodynamics-based predictions. Furthermore, these findings demonstrate the importance of investigating reaction pathways on graphene-based catalysts and other two-dimensional (2D) materials that involve metal active centers decorated by spectator intermediate species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Depinning of the ferroelectric domain wall in congruent LiNbO{sub 3}

The high coercive field, E{sub c}, of congruent LiNbO{sub 3} can be reduced by doping with Mg or Zn atoms, or by increasing the temperature above a threshold value. The physical origin for this reduction is not currently understood. Here, density functional theory calculations illustrate the atomic origin of the change in the switching field of the congruent LiNbO{sub 3}. They show that the high E{sub c} in the congruent LiNbO{sub 3} is a result of niobium antisite atoms on the lithium sublattice, pinning the motion of the domain walls. Thus, the healing of antisites by diffusion can significantly reduce the coercive field. In addition, this work demonstrates that the migration of these niobium antisites can be enhanced by doping or by changing the temperature. Thus, the depinning process of the congruent LiNbO{sub 3} is understood by the migration of the niobium antisite defect across the domain wall.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O{sub 2} adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N{sub 4} chelation, as well as the molecular and electronic structures for the O{sub 2} adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O{sub 2} on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d{sub z{sup 2}}, d{sub xy}, d{sub xz}, and d{sub yz}) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O{sub 2} adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ab initio study of phase stability of NaZr{sub 2}(PO{sub 4}){sub 3} under pressure

The elastic constants of NaZr{sub 2}(PO{sub 4}){sub 3} were computed as a function of pressure through Density Functional Theory calculations. The behavior of elastic constants show that the rhombohedral (R-3c) NaZr{sub 2}(PO{sub 4}){sub 3} becomes unstable above 8 GPa and is driven by softening of C{sub 44} through one of the Born stability criteria. High pressure equation of state and enthalpy show further that the ambient rhombohedral (R-3c)) NaZr{sub 2}(PO{sub 4}){sub 3} transforms first to another rhombohedral (R3) phase and subsequently to LiZr{sub 2}(PO{sub 4}){sub 3}-type orthorhombic phase at pressures above 6 and 8 GPa respectively which are in agreement with recent X-ray diffraction study.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Impact of incomplete metal coverage on the electrical properties of metal-CNT contacts: A large-scale ab initio study

Using a dedicated combination of the non-equilibrium Green function formalism and large-scale density functional theory calculations, we investigated how incomplete metal coverage influences two of the most important electrical properties of carbon nanotube (CNT)-based transistors: contact resistance and its scaling with contact length, and maximum current. These quantities have been derived from parameter-free simulations of atomic systems that are as close as possible to experimental geometries. Physical mechanisms that govern these dependences have been identified for various metals, representing different CNT-metal interaction strengths from chemisorption to physisorption. Our results pave the way for an application-oriented design of CNT-metal contacts.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

High‐Field NMR, Reactivity, and DFT Modeling Reveal the γ‐Al 2 O 3 Surface Hydroxyl Network**

Abstract Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ‐Al 2 O 3 is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ‐Al 2 O 3 at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high‐field 1 H and 27 Al solid‐state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular‐level structures of the active sites in catalytic alkane metathesis is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Storage and Effective Migration of Li-Ion for Defected β-LiFePO 4 Phase Nanocrystals

Lithium iron phosphate, a widely used cathode material, crystallizes typically in olivine-type phase, α-LiFePO4 (αLFP). However, the new phase β-LiFePO4 (βLFP), which can be transformed from αLFP under high temperature and pressure, is originally almost electrochemically inactive with no capacity for Li-ion battery, because the Li-ions are stored in the tetrahedral [LiO4] with very high activation barrier for migration and the one-dimensional (1D) migration channels for Li-ion diffusion in αLFP disappear, while the Fe ions in the β-phase are oriented similar to the 1D arrangement instead. In this work, using experimental studies combined with density functional theory calculations, we demonstrate that βLFP can be activated with creation of effective paths of Li-ion migration by optimized disordering. Thus, the new phase of βLFP cathode achieved a capacity of 128 mAh g–1 at a rate of 0.1 C (1C = 170 mA g–1) with extraordinary cycling performance that 94.5% of the initial capacity retains after 1000 cycles at 1 C. The activation mechanism can be attributed to that the induced disorder (such as FeLiLiFe antisite defects, crystal distortion, and amorphous domains) creates new lithium migration passages, which free the captive stored lithium atoms and facilitate their intercalation/deintercalation from the cathode. Such materials activated by disorder are promising candidate cathodes for lithium batteries, and the related mechanism of storage and effective migration of Li-ions also provides new clues for future design of disordered-electrode materials with high capacity and high energy density.

activation↗
DOE OSTI2015

Thermoelectric properties of IV–VI-based heterostructures and superlattices

Doping in a manner that introduces anisotropy in order to reduce thermal conductivity is a significant focus in thermoelectric research today. By solving the semiclassical Boltzmann transport equations in the constant scattering time (τ) approximation, in conjunction with ab initio electronic structure calculations, within Density Functional Theory, we compare the Seebeck coefficient (S) and figure of merit (ZT) of bulk PbTe to PbTe/SnTe/PbTe heterostructures and PbTe doping superlattices (SLs) with periodically doped planes. Bismuth and Thallium were used as the n- and p-type impurities, respectively. The effects of carrier concentration are considered via chemical potential variation in a rigid band approximation. The impurity bands near the Fermi level in the electronic structure of PbTe SLs are of Tl s- and Bi p-character, and this feature is independent of the doping concentration or the distance between impurity planes. We observe the impurity bands to have a metallic nature in the directions perpendicular to the doping planes, yet no improvement on the values of ZT is found when compared to bulk PbTe. For the PbTe/SnTe/PbTe heterostructures, the calculated S presents good agreement with recent experimental data, and an anisotropic behavior is observed for low carrier concentrations (n<10{sup 18} cm{sup −3}). A large value of ZT{sub ||} (parallel to the growth direction) of 3.0 is predicted for n=4.7×10{sup 18} cm{sup −3} and T=700 K, whereas ZT{sub p} (perpendicular to the growth direction) is found to peak at 1.5 for n=1.7×10{sup 17} cm{sup −3}. Both electrical conductivity enhancement and thermal conductivity reduction are analyzed. - Graphical abstract: Figure of merit for PbTe/SnTe/PbTe heterostructure along the [0 0 1] direction, P.D. Borges, J.E. Petersen, L. Scolfaro, H.W. Leite Alves, T.H. Myers, Improved thermoelectric properties of IV–VI-based heterostructures and superlattices. - Highlights: • Thermoelectric properties of IV–VI-based heterostructures and superlattices. • High figure of merit is predicted for the PbTe/SnTe/PbTe heterostructure. • Nanotechnology has an important role for the development of thermoelectric devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Recovery of edge states of graphene nanoislands on an iridium substrate by silicon intercalation

Finite-sized graphene sheets, such as graphene nanoislands (GNIs), are promising candidates for practical applications in graphene-based nanoelectronics. GNIs with well-defined zigzag edges are predicted to have spin-polarized edge-states similar to those of zigzag-edged graphene nanoribbons, which can achieve graphene spintronics. However, it has been reported that GNIs on metal substrates have no edge states because of interactions with the substrate. In this work, we used a combination of scanning tunneling microscopy, spectroscopy, and density functional theory calculations to demonstrate that the edge states of GNIs on an Ir substrate can be recovered by intercalating a layer of Si atoms between the GNIs and the substrate. We also found that the edge states gradually shift to the Fermi level with increasing island size. This work provides a method to investigate spin-polarized edge states in high-quality graphene nanostructures on a metal substrate.

density functional theory↗
DOE OSTI2014

Understanding time-resolved processes in atomic-layer etching of ultra-thin Al{sub 2}O{sub 3} film using BCl{sub 3} and Ar neutral beam

We scrutinize time-resolved processes occurring in atomic-layer etching (ALET) of ultra-thin Al{sub 2}O{sub 3} film using BCl{sub 3} gas and Ar neutral beam by employing density functional theory calculations and experimental measurements. BCl{sub 3} gas is found to be preferentially chemisorbed on Al{sub 2}O{sub 3}(100) in trans form with the surface atoms creating O-B and Al-Cl contacts. We disclose that the most likely sequence of etching events involves dominant detachment of Al-associated moieties at early etching stages in good agreement with our concurrent experiments on tracking Al{sub 2}O{sub 3} surface compositional variations during Ar bombardment. In this etching regime, we find that ALET requires half the maximum reaction energy of conventional plasma etching, which greatly increases if the etching sequence changes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Silica-copper catalyst interfaces enable carbon-carbon coupling towards ethylene electrosynthesis

Membrane electrode assembly (MEA) electrolyzers offer a means to scale up CO 2 -to-ethylene electroconversion using renewable electricity and close the anthropogenic carbon cycle. To date, excessive CO 2 coverage at the catalyst surface with limited active sites in MEA systems interferes with the carbon-carbon coupling reaction, diminishing ethylene production. With the aid of density functional theory calculations and spectroscopic analysis, here we report an oxide modulation strategy in which we introduce silica on Cu to create active Cu-SiO x interface sites, decreasing the formation energies of OCOH* and OCCOH*—key intermediates along the pathway to ethylene formation. We then synthesize the Cu-SiO x catalysts using one-pot coprecipitation and integrate the catalyst in a MEA electrolyzer. By tuning the CO 2 concentration, the Cu-SiO x catalyst based MEA electrolyzer shows high ethylene Faradaic efficiencies of up to 65% at high ethylene current densities of up to 215 mA cm -2 ; and features sustained operation over 50 h.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗