SEARCH · Engineering Papers

Results for “Density functional calculations”

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.

SourceResearch connectionFrom yearThrough year

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

At least 127 records · Page 7

All sources NASA NTRS DOE OSTI

DOE OSTI2022

Role of morphology in defect formation and photo-induced carrier instabilities in amorphous indium oxide

Ab initio molecular dynamics liquid-quench simulations and hybrid density functional calculations are performed to model the effects of room-temperature atomic fluctuations and photo-illumination on the structural and electronic properties of amorphous sub-stoichiometric In 2 O 2.96 . A large configurational ensemble is employed to reliably predict the distribution of localized defects as well as their response to the thermal and light activation. The results reveal that the illumination effects on the carrier concentration are greater in amorphous configurations with shorter In–O bond length and reduced polyhedral sharing as compared to the structures with a more uniform morphology. Further, the obtained correlation between the photo-induced carrier density and the reduction in the number of fully coordinated In-atoms implies that metal oxides with a significant fraction of crystalline/amorphous interfaces would show a more pronounced response to illumination. Photo-excitation also produces In–O 2 –In defects that have not been previously found in sub-stoichiometric amorphous oxides; these defects are responsible for carrier instabilities due to overdoping.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2026

Modeling an S N 2 Reaction Mechanism for Hydrolysis of Siloxane Linkages with Density Functional Theory under Basic Conditions and Implications for Dissolution of Quartz

An extended silicate molecular cluster was used to perform density functional theory calculations to determine if an S N 2 mechanism, where OH – attacks a Q 1 Si coupled with Na + charge balancing an adjacent siloxane bridging O atom, could explain the observed energy of activation of quartz dissolution under basic conditions.

chemical calculations↗

DOE OSTI2022

Evidence for electronic signature of a magnetic transition in the topological magnet HoSbTe

Topological insulators with intrinsic magnetic order are emerging as an exciting platform to realize fundamentally new excitations from topological quantum states of matter. To study these systems and their physics, people have proposed a variety of magnetic topological insulator systems, including HoSbTe, an antiferromagnetic weak topological insulator candidate. Here, in this work, we use scanning tunneling microscopy to probe the electronic structure of HoSbTe with antiferromagnetic and ferromagnetic orders that are tuned by applying an external magnetic field. Although around the Fermi energy we find minor differences between the quasiparticle interferences under the ferromagnetic and antiferromagnetic orders, deep inside the valance region, a quasiparticle interference signal emerges with ferromagnetism. This observation is consistent with our first-principles calculations indicating the magnetism-driven transition of the electronic states in this spin-orbit coupled topological magnet.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Formation energy puzzle in intermetallic alloys: Random phase approximation fails to predict accurate formation energies

We performed density functional calculations to estimate the formation energies of intermetallic alloys. We used two semilocal approximations, the generalized gradient approximation (GGA) by Perdew-Burke- Ernzerhof (PBE) and the strongly constrained and appropriately normed (SCAN) meta-GGA. In addition, we utilized two nonlocal DFT functionals, the hybrid HSE06, and the state-of-the-art random phase approximation (RPA). The nonlocal functionals such as HSE06 and RPA yield accurate formation energies of binary alloys with completely-filled d-band metals, where semilocal functionals underperform. The accuracy at the nonlocal functionals is greatly reduced when a partially-filled d-band metal is present in an alloy, while PBE-GGA outperforms in these cases. We show that the accurate prediction of formation energies by any DFT method depends on its ability to predict the accurate electronic properties, e.g., valence d-band contribution to the density of states (DOS). The SCAN meta-GGA often corrects the PBE-DOS, however, it does not provide accurate formation energies compared to PBE. This is assumed to be due to the lack of proper error cancellation that should be expected due to the similar bulk nature of both alloys and their constituents, which may improve with the modification of meta-GGA ingredients. RPA yields too negative formation energies of alloys with partially-filled d-band metals. RPA results can be corrected by restoring the exchange-correlation kernel, thereby improving the short-range electron-electron correlation in metallic densities.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Surface facet dependence of competing alloying mechanisms

Metal alloys are ubiquitous in many branches of heterogeneous catalysis, and it is now fairly well established that the local atomic structure of an alloy can have a profound influence on its chemical reactivity. While these effects can be difficult to probe in nanoparticle catalysts, model studies using well defined single crystal surfaces alloyed with dopants enable these structure–function correlations to be drawn. The first step in this approach involves understanding the alloying mechanism and the type of ensembles formed. In this study, we examined the atomic structure of RhCu single-atom alloys formed on Cu(111), Cu(100), and Cu(110) surfaces. Our results show a striking difference between Rh atoms alloying in Cu(111) vs the more open Cu(100) and Cu(110) surface facets. Unlike Cu(111) on which Rh atoms preferentially place-exchange with Cu atoms in the local regions above step edges leaving the majority of the Cu surface free of Rh, highly dispersed, homogeneous alloys are formed on the Cu(100) and (110) surfaces. These dramatically different alloying mechanisms are understood by quantifying the energetic barriers for atomic hopping, exchange, swapping, and vacancy filling events for Rh atoms on different Cu surfaces through theoretical calculations. Density functional theory results indicate that the observed differences in the alloying mechanism can be attributed to a faster hopping rate, relatively high atomic exchange barriers, and stronger binding of Rh atoms in the vicinity of step edges on Cu(111) compared to Cu(110) and Cu(100). Furthermore, these model systems will serve as useful platforms for examining structure sensitive chemistry on single-atom alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Equation of state of boron carbide B 4 ⁢C

We present the results of recent experiments conducted on the Sandia Z machine and a new tabular equation of state for B 4 ⁢C. The equation of state was calibrated to a combination of density functional calculations reported here and fits to preexisting data. It was constructed partly to recover the effects of a shock-driven, polymorphic phase transition of unknown character beginning at particle velocities of just under 3 km/s (shock pressures of 95 GPa). Some of the Z experiments included sound speeds determined by the overtaking rarefaction method, from which we calculate the Grüneisen parameter and compare with previous experiments conducted at the OMEGA laser [Fratanduono et al ., Phys. Rev. B 94 , 184107 (2016)], our own first principles calculations, and another recent tabular equation of state [Zhang et al ., Phys. Rev. E 102 , 053203 (2020)]. We also compare our results with previous static compression, thermophysical, and melt studies, finding mixed consistency. We predict the onset and completion of shock melting at 225 and 265 GPa, respectively, and predict a melt curve that is largely flat to pressures of several hundred GPa.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Li 8 MnO 6 : A Novel Cathode Material with Only Anionic Redox

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li 8 MnO 6 . This material is obtained by substituting Mn for Sn in Li 8 SnO 6 or for Zr in Li 8 ZrO 6 , and we also compare to previous work on those materials. The calculations predict that Li 8 MnO 6 is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O 2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li 8 MnO 6 formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li 8 MnO 6 cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

Li8MnO6↗

DOE OSTI2021

Origin of the magnetic and orbital ordering in α-Sr 2 CrO 4

Motivated by recent experimental progress in transition metal oxides with the K 2 NiF 4 structure, in this study we investigate the magnetic and orbital ordering in α-Sr 2 CrO 4 . Using first principles calculations, first we derive a three-orbital Hubbard model, which reproduces the ab initio band structure near the Fermi level. The unique reverse splitting of t 2g orbitals in α-Sr 2 CrO 4 , with the 3d 2 electronic configuration for the Cr 4+ oxidation state, opens up the possibility of orbital ordering in this material. Using real-space Hartree-Fock for multi-orbital systems, we constructed the ground state phase diagram for the two dimensional compound α-Sr 2 CrO 4 . We found stable ferromagnetic, antiferromagnetic, antiferro-orbital, and staggered orbital stripe ordering in robust regions of the phase diagram. Furthermore, using the density matrix renormalization group method for two-leg ladders with the realistic hopping parameters of α-Sr 2 CrO 4 , we explore magnetic and orbital ordering for experimentally relevant interaction parameters. Again, we find a clear signature of antiferromagnetic spin ordering along with antiferro-orbital ordering at moderate to large Hubbard interaction strength. We also explore the orbital-resolved density of states with Lanczos, predicting insulating behavior for the compound α-Sr 2 CrO 4 , in agreement with experiments. Finally, an intuitive understanding of the results is provided based on a hierarchy between orbitals, with d xy driving the spin order, while electronic repulsion and the effective one dimensionality of the movement within the d xz and d yz orbitals driving the orbital order.

36 MATERIALS SCIENCE↗

DOE OSTI2022

The Interaction of K and O 2 on Au(111): Multiple Growth Modes of Potassium Oxide and Their Catalytic Activity for CO Oxidation

Abstract In industrial catalysis, alkali cations are frequently used to promote activity or selectivity. Scanning tunneling microscopy, ambient‐pressure X‐ray photoelectron spectroscopy, and density‐functional calculations were used to study the structure and reactivity of potassium oxides in contact with the Au(111) surface. Three different types of oxides (K 2 O 2 , K 2 O and KO y with y <0.5) were observed on top of the gold substrate at 300–525 K. Initially, small aggregates of K 2 O 2 /K 2 O (1–2 nm in size) were seen at the elbows of the herringbone structure. After increasing the K coverage (>0.15 ML), large islands of the oxide (20–40 nm in size) appeared. These islands contained a mixture of K 2 O and KO y ( y <0.5). A key correlation was found involving the structure, oxidation state, and chemical activity of the alkali oxide. The small aggregates of potassium oxide had a very high catalytic activity for the oxidation of CO, being much more than plain promoters.

Shi, Rui↗

DOE OSTI2022

The Interaction of K and O 2 on Au(111): Multiple Growth Modes of Potassium Oxide and Their Catalytic Activity for CO Oxidation

Shi, Rui↗

DOE OSTI2021

Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with t BuNC and CO

The coordination of tBuNC and CO with the diarsenido complexes (C 5 Me 5 ) 2 An(η 2 -As 2 Mes 2 ), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of Th IV and U IV has been possible with CO; density functional calculations indicated an appreciable amount of π backbonding that originates from charge transfer from an actinide-arsenic sigma bond. The calculated CO stretching frequencies in the Th IV and U IV diarsenido complexes are consistent with the experimental measurements, both show large shifts to lower frequency. We demonstrate that the π backbonding is crucial to explaining the red shifts of CO frequency upon An IV complex formation. Interestingly, this interaction essentially correlates to the parallel orientation of π*(C-O) orbitals relative to the An-As bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2022

Bioinspired mechanically interlocking holey graphene@SiO 2 anode

Mechanically interlocking structures that can enhance adhesion at the interface and regulate the stress distribution have been widely observed in biological systems. Inspired by the biological structures in the wings of beetles, we synthesized a holey graphene@SiO 2 anode with strong mechanical interlocking, characterized it electrochemically, and explained its performance by finite element analysis and density functional calculations. The mechanically interlocking structure enhances lithium-ion (Li + ) storage by transmitting the strain from SiO 2 to the holey graphene and by a mechano-electrochemical coupling effect. The interlocking fit hinders the abscission of SiO 2 and the distinctive structure reduces the stress and strain of SiO 2 during (de)lithiation. The positive mechano-electrochemical coupling effect preserves the amount of electrochemically active phase (Li x Si) during cycles and facilitates Li + diffusion. Therefore, the capacity shows only a slight attenuation after 8000 cycles (cycling stability), and the specific capacity is ~1200 mA h g –1 at 5 A/g (rate-performance). This study furnishes a novel way to design high-performance Li + /Na + /K + /Al 3+ anodes with large volume expansion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Monolayer TiS 2 Nanosheets on Au(111)–Structural Characterization and Effect of Edge Stability for Shape Control

Transition metal dichalcogenides are promising alternatives to noble metal catalysts, e.g., for (photo-)activation of greenhouse gases or hydrogenations. Herein, a direct synthetic route for 2D TiS 2 nanosheets on Au(111) by titanium deposition in the presence of a mild, organic, non-oxidizing sulfur source is presented. High-resolution scanning tunneling microscopy (STM) is used to gain atomic-level insights into the TiS 2 nanosheet morphology. In contrast to the literature, this protocol gains mostly hexagonal and truncated triangular nanosheets with an increased edge contrast in STM, analog to metallic edge states in MoS 2 . Synchrotron-based photoelectron spectroscopy allows insights into compositional details, specifically to distinguish different S sites on the TiS 2 sheets and other S species on the sample. Further, a minimum size is identified (9 S atoms side length), which underlines the importance of moiré reconstructions for stress relief. The TiS 2 sheets coexist with [Au]Ti 1 S 3 clusters, in which a single gold atom is alloyed into the surface and capped by three S atoms. Together with the finding of a critical sheet size, this points toward on-surface Ostwald ripening as a relevant process in the sheet formation. Ab-initio calculations (density functional theory) underscore that the chemical potential of S is an essential descriptor to maintain shape control.

2D nanomaterials↗

DOE OSTI2024

Stabilizing lithium superoxide formation in lithium-air batteries by Janus chalcogenide catalysts

Solid lithium peroxide (Li 2 O 2 ) is the major discharge product in Li-air batteries. However, the electronically insulating nature of Li 2 O 2 tends to affect the battery’s performance such as the polarization gap and cyclability. On the other hand, lithium superoxide (LiO 2 ), generated through a one-electron transfer process, offers greater electronic conductivity, lower charge transfer resistance, and thus reduced charge potential. Nevertheless, LiO 2 long-term stabilization as a final product remains a significant challenge. Here, in this study, we present the molybdenum (Mo)-based Janus chalcogenide family featuring asymmetric structures as a new generation of cathode catalysts for Li-air batteries. These catalysts demonstrate remarkable efficacy in stabilizing LiO 2 discharge products, even under high current densities of 5000 mA/g (corresponding to 0.5 mA/cm 2 ). Our density functional calculations provide an understanding of why the asymmetric Mo-Janus chalcogenides result in LiO 2 formation whereas the symmetric Mo-dichalcogenides produce Li 2 O 2 as the discharge product. These results pave the way to explore a new generation of advanced catalysts for superoxide-based Li-air batteries.

Chalcogenide↗

DOE OSTI2020

Highly Active Rhenium-, Ruthenium-, and Iridium-Based Dichalcogenide Electrocatalysts for Oxygen Reduction and Oxygen Evolution Reactions in Aprotic Media

Transition metal dichalcogenides (TMDCs) have garnered much attention recently due to their remarkable performance for different electrochemical systems. In this study, we report on the synthesis and catalysis of less studied TMDC nanoflakes (NFs) with a design space comprised of three transition metals (rhenium, ruthenium, and iridium) and three chalcogens (sulfur, selenium, and tellurium) for the oxygen reduction and evolution reactions (ORR and OER) in an aprotic hybrid electrolyte containing 0.1 M lithium bis(trifluoromethanesulfonypimide salt in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid and dimethyl sulfoxide. Our results indicate that among the tested catalysts, ReS2 exhibits the highest current density for both ORR and OER, beyond those of the state-of-the-art catalysts used in aprotic media with Li salts. We performed density functional calculations to provide a mechanistic understanding of the reactions in the ReS2 NFs/ionic liquid system. These novel bifunctional catalyst results could open a way for exploiting the unique properties of these materials in Li-O-2 batteries as well as other important electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

The reaction of AnCl 4 (DME) n (An = Th, n = 2; U, n = 0) with 5 equiv of LiC 6 Cl 5 in Et 2 O resulted in the formation of homoleptic actinide-aryl “ate” complexes [Li(DME) 2 (Et 2 O)] 2 [Li(DME) 2 ][Th(C 6 Cl 5 ) 5 ] 3 ([Li][1]) and [Li(Et 2 O) 4 ][U(C 6 Cl 5 ) 5 ] ([Li][2]). Similarly, the reaction of AnCl 4 (DME)n (An = Th, n = 2; U, n = 0) with 3 equiv of LiC 6 Cl 5 in Et 2 O resulted in the formation of heteroleptic actinide-aryl “ate” complexes [Li(DME) 2 (Et 2 O)][Li(Et 2 O) 2 ][ThCl 3 (C 6 Cl 5 ) 3 ] ([Li][3]) and [Li(Et 2 O) 3 ][UCl 2 (C 6 Cl 5 ) 3 ] ([Li][4]). Density functional calculations show that the An–C ipso σ-bonds are considerably more covalent for the uranium complexes vs the thorium analogues, in line with past results. Additionally, good agreement between experiment and calculations is obtained for the 13 C ipso NMR chemical shifts in [Li][1] and [Li][3]. Here, the calculations demonstrate a deshielding by ca. 29 ppm from spin–orbit coupling effects originating at Th, which is a direct consequence of 5f orbital participation in the Th–C bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Vacancy-Driven Disorder and Elevated Dielectric Response in the Pyrochlore Pb 1.5 Nb 2 O 6.5

Lone pair-driven distortions are a hallmark of many technologically important lead (Pb)-based materials. Here, the role of Pb 2+ in polar perovskites is well understood and easily manipulated for applications in piezo- and ferroelectricity, but the control of ordered lone pair behavior in Pb-based pyrochlores is less clear. Crystallographically and geometrically more complex than the perovskite structure, the pyrochlore structure is prone to geometric frustration of local dipoles due to a triangular arrangement of cations on a diamond lattice. The role of vacancies on the O' site of the pyrochlore network has been implicated as an important driver for the expression and correlation of stereochemically active lone pairs in pyrochlores such as Pb 2 Ru 2 O 6.5 and Pb 2 Sn 2 O 6 . In this work we report on the structural, dielectric, and heat capacity behavior of the cation- and anion-deficient pyrochlore Pb 1.5 Nb 2 O 6.5 upon cooling. We find that local distortions are present at all temperatures that can be described by cristobalite-type cation ordering, and this ordering persists to longer length scales upon cooling. From a crystallographic perspective, the material remains disordered and does not undergo an observable phase transition. In combination with density function calculations, we propose that the stereochemical activity of the Pb 2+ lone pairs is driven by proximity to O' vacancies, and the crystallographic site disorder of the O' vacancies prohibits long range correlation of lone pair-driven distortions. This in turn prevents a low-temperature phase transition and results in an elevated dielectric permittivity across a broad temperature range.

36 MATERIALS SCIENCE↗