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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.

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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Dissociative electron attachment to amide bond containing molecules: N-ethylformamide and N-ethylacetamide

To advance our quest to understand the role of low energy electrons in biomolecular systems, we performed investigations on dissociative electron attachment (DEA) to gas-phase N-ethylformamide (NEF) and N-ethylacetamide (NEA) molecules. Both molecules contain the amide bond, which is the linkage between two consecutive amino acid residues in proteins. Thus, their electron-induced dissociation can imitate the resonant behavior of the DEA process in more complex biostructures. Our experimental results indicate that in these two molecules, the dissociation of the amide bond results in a double resonant structure with peaks at ~5 eV and 9 eV. We also determined the energy position of resonant states for several negative ions, i.e., the other dissociation products from NEF and NEA. Our predictions of dissociation channels were supported by density functional theory calculations of the corresponding threshold energies. Our results and those previously reported for small amides and peptides imply the fundamental nature for breakage of the amide bond through the DEA process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Spin qubit properties of the boron-vacancy/carbon defect in the two-dimensional hexagonal boron nitride

Spin qubit defects in two-dimensional materials have a number of advantages over those in three-dimensional hosts including simpler technologies for defect creation and control, as well as qubit accessibility. In this work, we select the V B C B defect in the hexagonal boron nitride (hBN) as a possible optically controllable spin qubit and explain its triplet ground state and neutrality. In this defect a boron vacancy is combined with a carbon dopant substituting the closest boron atom to the vacancy. Our density-functional-theory calculations confirmed that the system has dynamically stable spin triplet and singlet ground states. As revealed from our linear response GW calculations, the spin-sensitive electronic states are localized around the three undercoordinated N atoms and make local peaks in the density of electronic states within the bandgap. Using the triplet and singlet ground state energies, as well as the energies of the optically excited states, obtained from solution to the Bethe–Salpeter equation, we construct the spin-polarization cycle, which is found to be favorable for the spin qubit initialization. The calculated zero-field splitting parameters ensure that the splitting energy between the spin projections in the triplet ground state is comparable to that of the known spin qubits. We thus propose the V B C B defect in hBN as a promising spin qubit.

2D BN↗
DOE OSTI2024

Low-temperature etching of silicon oxide and silicon nitride with hydrogen fluoride

Etching of high aspect ratio features into alternating SiO 2 and SiN layers is an enabling technology for the manufacturing of 3D NAND flash memories. In this paper, we study a low-temperature or cryo plasma etch process, which utilizes HF gas together with other gas additives. Compared with a low-temperature process that uses separate fluorine and hydrogen gases, the etching rate of the SiO 2 /SiN stack doubles. Both materials etch faster with this so-called second generation cryo etch process. Pure HF plasma enhances the SiN etching rate, while SiO 2 requires an additional fluorine source such as PF 3 to etch meaningfully. Further, the insertion of H 2 O plasma steps into the second generation cryo etch process boosts the SiN etching rate by a factor of 2.4, while SiO 2 etches only 1.3 times faster. We observe a rate enhancing effect of H 2 O coadsorption in thermal etching experiments of SiN with HF. Ammonium fluorosilicate (AFS) plays a salient role in etching of SiN with HF with and without plasma. AFS appears weakened in the presence of H 2 O. Density functional theory calculations confirm the reduction of the bonding energy when NH 4 F in AFS is replaced by H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ghost states and surface structures of the charge density wave kagome metal ScV 6 Sn 6

In this work, we investigate the high-temperature phase of the kagome metal ScV 6 Sn 6 using scanning tunneling microscopy/spectroscopy (STM/S) and density functional theory calculations. STM topographic images of the cleaved sample reveal two distinct surface terminations: flat islands with Sn termination and trenches terminated by kagome layers with Sn as the outermost atomic layer. STS measurements on the Sn-terminated and kagome-terminated surfaces show significant differences, in particular the presence of large density of states near the Fermi level in the former case. Our first-principles calculations reveal that the charge density on the kagome-terminated surface gives rise to “ghost states” which show intensity away from surface atoms, arising due to hybridization of orbitals above the surface. These states can obscure the intrinsic properties of the surface, potentially leading to misattribution of the surface termination. This underscores the need for careful interpretation in STM studies, especially when discerning surface states of localized states. Understanding the surface structure of this versatile quantum material provides essential information for interpreting surface-sensitive experiments, tailoring material properties, engineering interfaces, and controlling stability and reactivity. This knowledge paves the way for further exploration and potential applications of kagome lattice materials in various fields, including quantum computing, topological physics, and advanced electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Hollow-structured Ni-N-C catalysts for highly selective CO 2 electroreduction

Atomically dispersed single-atom catalysts have emerged as promising non-precious catalyst alternatives to expensive Ag and Au catalysts for electrochemical CO 2 reduction reaction (CO 2 RR). In particular, nickel-nitrogen-carbon (Ni-N-C) catalysts have demonstrated a high faradaic efficiency (FE) toward CO formation at low overpotentials. Nonetheless, the exact nature of Ni active sites under CO 2 RR remains elusive and conventional Ni-N-C catalysts are limited by microporosity and low density of Ni single atoms, hindering performance in CO 2 electrolyzers. Here, we report the synthesis of hollow-structured Ni-N-C ( hs -Ni-N-C) catalysts via a post-synthesis modification (PSM) strategy using partial ligand exchange of 2-methylimidazole with 3-amino-1,2,4-triazole. This approach enables the formation of a hollow structure, resulting in more than a twofold increase in Ni atom density compared to regular Ni-N-C (r-Ni-N-C). In a zero-gap CO 2 electrolyzer, the optimized hs -Ni-N-C allows for achieving an FE CO of 97% at a current density of > 100 mA cm⁻ 2 , while maintaining high CO selectivity with stable performance over 100 h at 2.5 V. hs-Ni-N-C shows a more than sevenfold increase in the CO partial current density relative to r-Ni-N-C resulting from the combined effects of a higher density of Ni single-atom sites, improved kinetics, and lower transport resistance under the operating conditions, as indicated by electrochemical impedance spectra and distribution of relaxation times analysis. Operando high energy-resolution X-ray absorption spectroscopy (XAS) reveals that atop-bonded CO on Ni single sites induces dynamic transformations of the Ni–N coordination environment, leading to a symmetric coordination structure of hs -Ni-N-C. Under CO 2 RR, the catalysts undergo a more pronounced structural change and form a minor fraction of Ni nanoparticles. Density functional theory calculations are consistent with the XAS results and provide molecular insights showing that the interplay between protonation and CO adsorption leads to adsorbate-induced restructuring of the Ni single atom. This work demonstrates the synergistic role of hollow structure and high-density Ni atoms in governing CO 2 RR selectivity and provides mechanistic insights into the structural dynamics of single-atom catalysts under operating conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

An improved oxygen reduction reaction activity and CO 2 -tolerance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ achieved by a surface modification with barium cobaltite coatings

Solid oxide fuel cells (SOFCs) cathode often suffers from the poisoning effect of the contaminants commonly encountered in air such as CO 2 . Here we report an effective approach to enhancing the activity and CO 2 tolerance of the state-of-the-art La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) cathode enabled by a coating of BaCoO 3-δ (BCO), as verified by the electrochemical testings, Raman analyses, and density functional theory calculations. When surface modified with a thin-film BCO coating, LSCF displays a much enhanced ORR activity and an improved durability against CO 2 . For example, anode supported SOFCs with the LSCF cathode coated with BCO coatings show a remarkable peak power density (Pmax) of 0.41 Wcm -2 and a significantly reduced degradation rate in current density of ~0.08% h -1 at 0.8 V and 700 °C for a period of 300 hs when humidified H2 (with 3 vol%H2O) was used as fuel and air with 8 vol% CO 2 as oxidant. The demonstrated performance is improved when compared with those of the cells with a blank LSCF electrode (a Pmax of ~0.36 Wcm -2 and a degradation rate of ~0.15% h -1 ) under the same conditions. Furthermore, the adsorption energy calculations suggests that BCO coating makes CO 2 adsorption much weaker than LSCF (-0.54 eV versus -1.07 eV).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Toward an accurate equation of state and B1-B2 phase boundary for magnesium oxide up to terapascal pressures and electron-volt temperatures

By applying auxiliary-field quantum Monte Carlo, we calculate the equation of state (EOS) and B1-B2 phase transition of magnesium oxide (MgO) up to 1 TPa. Here, the results agree with available experimental data at low pressures and are used to benchmark the performance of various exchange-correlation functionals in density functional theory calculations. We determine PBEsol is an optimal choice for the exchange-correlation functional and perform extensive phonon and quantum molecular-dynamics calculations to obtain the thermal EOS. Our results provide a preliminary reference for the EOS and B1-B2 phase boundary of MgO from zero up to 10,500 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts

Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.

1-hexyne↗
DOE OSTI2021

Shedding Light on Primary Donors in Photosynthetic Reaction Centers

Chlorophylls (Chl)s exist in a variety of flavors and are ubiquitous in both the energy and electron transfer processes of photosynthesis. The functions they perform often occur on the ultrafast (fs–ns) time scale and until recently, these have been difficult to measure in real time. Further, the complexity of the binding pockets and the resulting protein-matrix effects that alter the respective electronic properties have rendered theoretical modeling of these states difficult. Recent advances in experimental methodology, computational modeling, and emergence of new reaction center (RC) structures have renewed interest in these processes and allowed researchers to elucidate previously ambiguous functions of Chls and related pheophytins. This is complemented by a wealth of experimental data obtained from decades of prior research. Studying the electronic properties of Chl molecules has advanced our understanding of both the nature of the primary charge separation and subsequent electron transfer processes of RCs. In this review, we examine the structures of primary electron donors in Type I and Type II RCs in relation to the vast body of spectroscopic research that has been performed on them to date. Further, we present density functional theory calculations on each oxidized primary donor to study both their electronic properties and our ability to model experimental spectroscopic data. This allows us to directly compare the electronic properties of hetero- and homodimeric RCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Potential high-performance magnet materials: Co- and Al-alloyed Sm 2 Fe 17

Sm 2 Fe 17 has long been known as a potential high-performance magnet whose deficiencies—planar anisotropy and lower-than-optimal T c —can be remedied by nitrogen addition, but which presents synthesis difficulties. In this work, we apply first-principles calculations to search for alternative low-cost, high-performance permanent magnets in this family, by exploring simultaneous Fe and Al substitution. Specifically, the goal is to improve properties of Sm 2 Fe 14 Al 3 easy-plane magnet at the stoichiometric composition. Density functional theory calculations were executed for three series of compounds, i.e., Sm 2 (Fe 1-x Co x ) 14 Al 3 , Sm 2 (Fe 1-x Co x ) 15 Al 2 , and Sm 2 (Fe 1-x Cox) 16 Al. We find that substitution of Fe with 12–18 of Co in % Sm 2 Fe 14 Al 3 modifies the magnetic anisotropy type from easy plane to easy axis with a substantial anisotropy of 7.1 MJ/m 3 . We also demonstrate that the largest part of magnetic anisotropy is introduced by 4f Sm atom electrons. Thus the rotation of magnetic moment orientation from $\langle$$1\bar10$$\rangle$ to $\langle$111$\rangle$ is followed by an increase of the occupied 4f state number and, as a result, the orbital part of the magnetic moment of one of the Sm atoms. This increase of the occupied 4f state number at an energy ~ -4.3 eV results in a significant reduction of band structure energy. The substitution of Fe by Co does not significantly reduce the magnetization of the compound and keeps it slightly above 1 T. This combination of magnetic anisotropy and magnetization makes the compound a promising candidate for a permanent magnet.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Predicting phase transitions in PbTi⁢O 3 using zentropy through quasiharmonic phonon calculations

According to x-ray diffraction (XRD) measurements, PbTi⁢O 3 undergoes a phase transition from a tetragonal ferroelectric (FE) phase to a cubic paraelectric phase at 763 K. However, x-ray absorption fine-structure (XAFS) measurements indicate that PbTi⁢O 3 is locally tetragonal even after the phase transition. The difference in these results is because XAFS measurements can probe local features of a structure, while XRD averages over such local features. For both measurements to be consistent, PbTi⁢O 3 is macroscopically cubic but locally tetragonal after the phase transition. Despite this, most models, such as the Landau-Ginsburg-Devonshire theory and effective Hamiltonians, are still unable to explain this phenomenon. Moreover, these methods involve model parameters fitted to experimental or theoretical data and do not consider other tetragonal configurations, such as domain walls, to predict the phase transition. In our previous study, we used our zentropy approach to predict the phase transition by considering the tetragonal FE ground-state configuration and the tetragonal 90° and 180° domain wall configurations with their total energies at 0 K. Here, in this paper, the Helmholtz energies of the three configurations are obtained from density functional theory calculations through energy-volume curves and phonon calculations. The predicted phase transition temperature using the meta-GGA 𝑟 2⁢ SCAN and revised multiplicities of configurations is 716 K, showing good agreement with the experimental value of 763 K.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Protein C-GeM: A Coarse-Grained Electron Model for Fast and Accurate Protein Electrostatics Prediction

The electrostatic potential (ESP) is a powerful property for understanding and predicting electrostatic charge distributions that drive interactions between molecules. In this study, we compare various charge partitioning schemes including fitted charges, density-based quantum mechanical (QM) partitioning schemes, charge equilibration methods, and our recently introduced coarse-grained electron model, C-GeM, to describe the ESP for protein systems. Furthermore, when benchmarked against high quality density functional theory calculations of the ESP for tripeptides and the crambin protein, we find that the C-GeM model is of comparable accuracy to ab initio charge partitioning methods, but with orders of magnitude improvement in computational efficiency since it does not require either the electron density or the electrostatic potential as input.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tailoring the structural durability and proton conductivity of electrolytes for highly fuel-flexible and reversible ceramic cells

A durable and high ionic conducting electrolyte is critical for achieving fuel-flexible and reversible protonic ceramic cells (PCCs) at reduced temperatures since the developed electrolyte materials are vulnerable to steam, CO 2 , or coking deterioration. Here, we report a fast-conducting electrolyte material BaZr 0.06 Ce 0.7 Y 0.06 Yb 0.06 Hf 0.06 Gd 0.06 O 3−δ (BZCYYbHG), demonstrating excellent durability against CO 2 and H 2 O under the realistic electrolysis operations, and a high conductivity of 0.017 S cm −1 at 550 °C for lowering the PCC operating temperature. Further, density functional theory calculations indicate that the higher configurational entropy of mixing at the B-site cations slightly reduces the hydrogen adsorption energy, suggesting a higher incorporation rate of protons or hydrogen atoms into the electrolyte bulk. Ultimately, single cells with the BZCYYbHG electrolyte deliver peak power densities of 1.39, 1.12, and 0.7 W cm −2 in H 2 , NH 3 , and wet CH 4 at 550 °C with promising durability. In addition, the PCCs achieve a current density of −1.61 A cm −2 at 1.3 V and 550 °C with a high faradaic efficiency of 91.3% at −0.5 A cm −2 , enabling stable operations in steam electrolysis mode under humid air (30% H 2 O), wet air containing CO 2 (up to 10%), and reversible cycling.

25 ENERGY STORAGE↗
DOE OSTI2026

Understanding Inlet Concentration Effects on the Electrocatalytic Conversion of CO 2 to Formic Acid in Gas-Fed Electrolyzers

The electrochemical CO 2 reduction reaction (CO2RR) to produce value-added products remains a developing technology for utilizing waste CO 2 streams. Most device-level CO2RR studies use pure CO 2 gas feeds; however, the effect of dilute CO 2 on the electrolyzer performance is an important consideration for large-scale electrolyzer operation, single-pass conversion, and real-world CO 2 source utilization. This work investigates the effect that the CO 2 concentration has on the performance of formic acid (HCOOH) producing tin oxide (SnO 2 ) and bismuth oxide (Bi 2 O 3 ) catalysts in an electrolyzer device setting. Surprisingly, SnO2 demonstrated an approximately 20% increase in HCOOH selectivity (Faradaic efficiency) when the CO 2 concentration decreased from 100 to 20%. In contrast, Bi 2 O 3 consistently demonstrated high selectivity toward HCOOH across the same CO 2 concentration range. The effects of the CO 2 concentration on selectivity were further investigated with half-cell experiments and in situ Raman spectroscopy, which revealed dynamic changes in the cathodic overpotential and chemical state of the catalyst that depended on the CO 2 concentration. Density functional theory calculations showed how changes in the surface oxidation state of Sn, varying from fully oxidized SnO 2 to metallic Sn(0), affect the thermodynamic barriers of the three main observed products: HCOOH, CO, and H 2 . Our results indicate that dilute CO 2 concentrations required larger cathodic overpotentials to sustain a fixed current density, which, in turn, pushed the Sn-based catalyst toward a more reduced surface that was favorable to HCOOH formation. On the other hand, the Bi-based catalyst remained in a metallic state at CO2RR-relevant potentials and demonstrated a consistent product selectivity regardless of CO 2 concentration. These findings highlight how varying the CO 2 inlet gas concentrations affects the chemical state of catalysts and the resulting performance metrics.

42 ENGINEERING↗
DOE OSTI2020

Thermodynamics and Magnetism of YCo5 Compound Doped with Fe and Ni: An Ab Initio Study

YCo5 permanent magnet exhibits high uniaxial magnetocrystalline anisotropy energy and has a high Curie temperature. These are good properties for a permanent magnet, but YCo5 has a low energy product, which is notably insufficient for a permanent magnet. In order to improve the energy product in YCo5, we suggest replacing cobalt with iron, which has a much bigger magnetic moment. With a combination of density-functional-theory calculations and thermodynamic CALculation of PHAse Diagrams (CALPHAD) modeling, we show that a new magnet, YFe3(Ni1-xCox)2, is thermodynamically stable and exhibits an improved energy product without significant detrimental effects on the magnetocrystalline anisotropy energy or the Curie temperature.

anisotropy↗
DOE OSTI2022

Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks

We report two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn 2+ with a stronger Lewis acidic Co 2+ , leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electronic and Vibrational Contributions to the Bulk Stabilities of Trivalent 3d Transition Metal Oxyhydroxides from Electronic Structure Calculations

Any understanding of the thermodynamic driving forces active in the global cycles of earth abundant metals requires attendant knowledge of the bulk mineral free energies. This can be particularly challenging for metal (oxyhydr)oxide phases which at low temperature aqueous conditions can be produced at a variety of hydration states and particle sizes. Here we present high quality density functional theory calculations of the relative bulk stabilities of a geologically important family of polymorphic trivalent metal oxyhydroxide crystal structures MOOH (M=Cr, Al, Fe). To improve understanding of their relative stabilities we permute the metal cations into the various possible canonical structure types including goethite (isostructural to diaspore and bracewillite), lepidocrocite (isosctructural to boehmite), guyaniite, and grimaldiite. Electronic, vibrational, and magnetic contributions are considered on a consistent theoretical footing using hybrid functionals and converged plane-wave bases. We find the considered bulk structures to be thermodynamically degenerate within the precision of the available theory, despite the fact that the vibrational and magnetic contributions vary substantially among the cations. A significant conclusion is that Cr3+ supports strong hydrogen bonds, low O-H stretching frequencies and facile H movement relative to the other cations.

Prange, Micah P.↗