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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Optimized Auxiliary Functions for Robust Mitigation of Finite-Size Errors in Periodic Hybrid Density Functional Theory

When calculating properties of periodic systems at the thermodynamic limit (TDL), the dominant source of finite size error (FSE) arises from the long-range Coulomb interaction, and can manifest as a slowly converging quadrature error when approximating an integral in the reciprocal space by a finite sum. The singularity subtraction (SS) method offers a systematic approach for reducing this quadrature error and thus the FSE. Here, in this work, we first investigate the performance of the SS method in the simplest setting, aiming at reducing the FSE in exact exchange calculations by subtracting the Coulomb contribution with a single, adjustable Gaussian auxiliary function. We demonstrate that a simple fitting method can robustly estimate the optimal Gaussian width and leads to rapid convergence toward the TDL. Furthermore, we suggest new forms of the auxiliary function, whose optimal parameters could also be determined through least-squares fitting. For a range of semiconductors and insulators, the proposed auxiliary functions achieve robust, millihartree-level accuracy in hybrid density functional theory calculations, including cases with sparse k-meshes and large basis sets.

Quiton, Stephen Jon [University of California, Ber↗
DOE OSTI2020

Rethinking the magnetic properties of lepidocrocite: A density functional theory and cluster expansion study

The iron oxyhydroxide lepidocrocite (g-FeOOH) is an abundant mineral critical to a number of chemical and technological applications. Of particular interest is the ground state and nite temperature magnetic order, and the subsequent impact this has upon crystal properties. The magnetic properties, investigated in this work are governed primarily through superexchange interactions, and have been calculated using density functional theory and cluster expansion methods. Quantication of these exchange terms has facilitated the determination of the ground state magneto-crystalline structure and subsequent calculation of its lattice constants, elastic moduli, cohesive enthalpy, and electronic density of states. Further, using a collinear magnetic conguration model, the magnetic heat capacity versus temperature has been studied and the Neel temperature obtained.

Pope, Daniel J.↗
DOE OSTI2025

Unconventional Anomalous Hall Effect in Hexagonal Polar Magnet Y 3 Co 8 Sn 4

A rare realization of unconventional anomalous Hall effect (UAHE) both below and above the magnetic transition temperature (T C ) in a hexagonal noncentrosymmetric magnet Y 3 Co 8 Sn 4 , using a combined experimental and ab initio calculations. Occurrence of such UAHE is mainly attributed to the reciprocal ($\mathscr{KS}$) topology (i.e., the presence of topological Weyl points at/near the Fermi level), along with some contribution from the topological magnetic texture (at low temperatures), as inferred from the measured field-dependent ac susceptibility. The effect of UAHE on the measured transport behavior however evolves differently with temperature above and below T C = 53 K, suggesting different physical mechanism responsible in the two phases. A unique planar ferrimagnetic ordering is found to be the most stable state with ab-plane as the easy plane below T C . The simulated net magnetization and the moment per Co atom agrees fairly well with the experimentally measured values. A reasonably large anomalous Hall conductivity (AHC) is also observed in both the phases (above and below T C ) of the present compound, which is again not so ubiquitous. In conclusion, the results underscore the family of R 3 Co 8 Sn 4 (R = rare earth) polar magnets as a compelling backdrop for exploring the synergy of magnetism and topological non-trivial electronic states, pivotal for spintronic applications.

Density functional theory calculations↗
DOE OSTI2021

Thermodynamics and kinetics of H adsorption and intercalation for graphene on 6 H -SiC(0001) from first-principles calculations

Previous experimental observations for H intercalation under graphene on SiC surfaces motivate the clarification of configuration stabilities and kinetic processes related to intercalation. From first-principles density-functional-theory calculations, we analyze H adsorption and intercalation for graphene on a 6H-SiC(0001) surface, where the system includes two single-atom-thick graphene layers: the top-layer graphene (TLG) and the underling buffer-layer graphene (BLG) above the terminal Si layer. Our chemical potential analysis shows that in the low-H coverage regime (described by a single H atom within a sufficiently large supercell), intercalation into the gallery between TLG and BLG or into the gallery underneath BLG is more favorable thermodynamically than adsorption on top of TLG. However, intercalation into the gallery between TLG and BLG is most favorable. We obtain energy barriers of about 1.3 and 2.3 eV for a H atom diffusing on and under TLG, respectively. From an additional analysis of the energy landscape in the vicinity of a step on the TLG, we assess how readily one guest H atom on the TLG terrace can directly penetrate the TLG into the gallery between TLG and BLG versus crossing a TLG step to access the gallery. Finally, we also perform density functional theory calculations for higher H coverages revealing a shift in favorability to intercalation of H underneath BLG and characterizing the variation with H coverage in interlayer spacings.

36 MATERIALS SCIENCE↗
DOE OSTI2025

d -Electron Heavy Fermion Behavior in a Near-Room-Temperature Polar Metallic Ferrimagnet: A Case of Mn 5 SiC

Polycrystalline Mn 5 SiC was synthesized by using a high-temperature solid-state method. Mn 5 SiC adopts a polar space group (Cmc2 1 ) with six crystallographic Mn sites confirmed by X-ray and neutron diffraction, transmission electron microscopy, and second harmonic generation experiments. The complex crystal structure features edge-sharing trigonal prisms and icosahedra, as well as face/edge-sharing pentagonal prisms. Magnetic measurements indicate ferrimagnetic ordering with a transition temperature of 284 K. The ferrimagnetic structure (magnetic space group Cm’c’2 1 ) was further identified by powder neutron diffraction, where collinear Mn spins align along the crystallographic c-axis. The refined magnetic moment for each crystallographic Mn site at 4 K is 1.8(2), −2.42(9), −1.72(8), 0.51(6), 0.50(4), and 1.7(2) μ B . Density functional theory calculations confirm both the metallic behavior and the ferrimagnetic structure observed experimentally and further provide insight into the observed Mn moment dependence across crystallographic sites. The resistivity and specific heat measurements and density functional theory calculations reveal a substantially large Kadowaki–Woods ratio of 5 × 10 –5 μΩ·cm/(mJ/mol) 2 and a many-body renormalization factor of 5.5, indicating the unusual heavy Fermion behavior in such an itinerant magnetic metal.

Messegee, Zachary T. [George Mason University, Fai↗
DOE OSTI2021

CHARGED POINT DEFECTS AND DEFECT COMPLEXES IN PHOSPHORENE AND STRUCTURAL PREDICTION OF TAU-11, A DENSITY FUNCTIONAL THEORY APPROACH

With the advent of powerful computers, first principle calculations have become a robust and reliable tool to complement experiments in the study of materials. First principle calculations such as density functional theory can be used to guide experiments to save time and effort when it comes to new and advanced materials discovery. Study of charge defects in materials and crystal structure prediction are such areas in which density functional theory calculations facilitate the prediction of defect formation energy, charge transition levels and elemental site occupations. Experimentally, studying charge defects requires inferring results from various techniques. Likewise, determining site occupancies for similar elements using experimental techniques is challenging and sometimes impossible. In this work, we study the charged intrinsic and extrinsic defects and defect complexes in phosphorene and determine the site occupancies of Al, Fe and Si in the τ11 phase using density functional theory. In the defect work, we calculate the defect formation energy, charge transition level, binding energies and Stokes shift for vacancy, dopant substitution and dopant-vacancy defect complexes in phosphorene. We found that vacancy defect in phosphorene becomes negatively charged in n-type doping and may passivate the dopants and reduce carrier concentration and mobility. For non-metal dopants in phosphorene, we predict that O, S and Si prefer to form dopant-vacancy complexes removing the vacancy defect states from the band gap. Mn dopant-vacancy defect complex exhibits possibility of switching between two magnetic spin states. Lastly, using density functional theory, we complement the results from neutron powder diffraction to determine the site occupancies of Al and Si in τ11 phase which was used to determine the alloying element to develop a high temperature and low density alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Phonon Olympics: Phonon property and lattice thermal conductivity benchmarking from open-source packages

Three widely used open-source packages for determining phonon properties and lattice thermal conductivities (ALAMODE, phono3py, and ShengBTE) are benchmarked by teams of expert users and the package developers. The phonons for Ge, RbBr, monolayer MoSe 2 , and AlN are modeled at zero temperature, and they scatter through three-phonon and phonon-isotope processes, with thermal conductivities obtained from the linearized Peierls–Boltzmann transport equation with input from density functional theory calculations. Over a wide range of temperatures, the thermal conductivities calculated by the teams fall within at most ±15% of their mean values for each of the four materials. The phonon frequencies, obtained from the harmonic force constants, do not show large differences between the calculations, indicating that the modal heat capacities and group velocities are not responsible for the thermal conductivity variations. It is the lifetimes associated with three-phonon scattering, obtained from the cubic force constants, that drive the variations. The many decisions required to calculate the cubic force constants (e.g., supercell size, atomic displacement, neighbor cutoff, and application of symmetries) make identification of the precise origin of the thermal conductivity variations challenging. The calculated thermal conductivities do not generally show agreement with experimental measurements, which is attributed to the limitations of the density functional theory calculations. Guidance for the development of best practices is provided, which will help to standardize protocols needed for building thermal conductivity databases. The results provide a baseline for future benchmarking of other packages and more advanced calculations.

McGaughey, Alan J. H. [Carnegie Mellon Univ., Pitt↗
DOE OSTI2021

Finite-size correction for slab supercell calculations of materials with spontaneous polarization

Abstract The repeated slab approach has become a de facto standard to accurately describe surface properties of materials by density functional theory calculations with periodic boundary conditions. For materials exhibiting spontaneous polarization, we show that the conventional scheme of passivation with pseudo hydrogen is unable to realize a charge-neutral surface. The presence of a net surface charge induces via Gauss’s law a macroscopic electric field through the slab and results in poor size convergence with respect to the thickness of the slab. We propose a modified passivation method that accounts for the effect of spontaneous polarization, describes the correct bulk limits and boosts convergence with respect to slab thickness. The robustness, reliability, and superior convergence of energetics and electronic structure achieved by the proposed method are demonstrated using the example of polar ZnO surfaces.

Chemistry↗
DOE OSTI2025

Constraints on magnetism and correlations in RuO 2 from lattice dynamics and Mössbauer spectroscopy

We provide experimental evidence for the absence of a magnetic moment in bulk RuO 2 , a candidate altermagnetic material, by using a combination of Mössbauer spectroscopy, nuclear forward scattering, inelastic X-ray and neutron scattering, and density functional theory calculations. Using complementary Mössbauer and nuclear forward scattering, we determine the Ru magnetic hyperfine splitting to be negligible. Inelastic X-ray and neutron scattering-derived lattice dynamics of RuO 2 are compared to density functional theory calculations of varying flavors. Comparisons among theory with experiments indicate that electronic correlations, rather than magnetic order, are key in describing the lattice dynamics.

Mössbauer spectroscopy↗
DOE OSTI2023

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Zhou, Jiahua↗
DOE OSTI2021

A Polar Magnetic and Insulating Double Corundum Oxide: Mn2MnSbO6 with Ordered Mn(II) and Mn(III) Ions

A new magnetic insulator Mn2MnSbO6 with a polar crystal structure and an ordered Mn2+ and Mn3+ arrangement was synthesized under a high pressure of 7.5 GPa and 1300 degrees C. The crystal structure of Mn2MnSbO6, investigated by synchrotron powder X-ray diffraction, was found to be isomorphous with that of Ni3TeO6-type, space group R3. The non-centrosymmetric structure was confirmed by the second-harmonic generation measurements. The X-ray absorption near-edge spectroscopy measurement confirmed the nominal oxidation states of Mn22+Mn3+SbO6. Magnetic measurements indicate that Mn2MnSbO6 orders antiferromagnetically below 44 K and undergoes a field-induced spin-flop transition at 5 K. First-principles calculations indicate an antiferromagnetic ground state with up/up/up/down/down/down (uuuddd) spin configuration of the six crystallographically unique Mn ions in the c-axis doubled magnetic structure. The density functional theory calculations also substantiate the experimentally observed charge ordering of the Mn2+/Mn3+ ions and the insulating behavior due to a bandgap of 0.52 eV. To the best of our knowledge, this is the first double corundum oxide containing Jahn-Teller active Mn3+ ions.

Feng, Hai L.↗
DOE OSTI2020

Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces

Electrochemical kinetics at electrode–electrolyte interfaces limit the performance of devices including fuel cells and batteries. While the importance of moving beyond Butler–Volmer kinetics and incorporating the effect of electronic density of states of the electrode has been recognized, a unified framework that incorporates these aspects directly into electrochemical performance models is still lacking. In this work, we explicitly account for the density functional theory-calculated density of states numerically in calculating electrochemical reaction rates for a variety of electrode–electrolyte interfaces. We first show the utility of this for two cases related to Li metal electrodeposition and stripping on a Li surface and a Cu surface (anode-free configuration). The deviation in reaction rates is minor for cases with flat densities of states such as Li, but is significant for Cu due to nondispersive d-bands creating large variation. Finally, we consider a semiconducting case of a solid-electrolyte interphase consisting of LiF and Li2CO3 and note the importance of the Fermi level at the interface pinned by the redox reaction occurring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach.

Kurchin, Rachel (ORCID:0000000221474809)↗
DOE OSTI2024

Point defects and doping in wurtzite LaN

Wurtzite LaN (wz-LaN) is a semiconducting nitride that has piezoelectric and ferroelectric properties, making it promising for applications in electronics, either as a binary compound or in alloys such as LaAlN. The prospects for wz-LaN in devices are influenced by the properties of point defects and impurities; here, we use first-principles density functional theory with a hybrid functional to calculate their formation energies, as well as their atomic and electronic structures. Among native point defects, we find that nitrogen-related defects, both vacancies ($V^+_N$) and interstitials ($N^-_i$), are energetically most favorable under most relevant chemical potentials and positions of the Fermi level; $V^0_N$ may additionally be observed under N-poor conditions, and $N^0_i$ may be prominent under N-rich conditions. We also investigate the incorporation of oxygen and hydrogen, which will likely be present as unintentional impurities. We find that the $O^+_N$ substitutional species readily forms, but oxygen will not lead to n-type conductivity due to formation of DX centers and compensation by interstitial defects. Similarly, substitutional HN and interstitial H i can compensate both p- and n-type dopants. Our results provide detailed, microscopic guidance for the development of electronic devices based on wz-LaN.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Trivial to nontrivial topology transition in rare-earth pnictides with epitaxial strain

The combination of magnetotransport and topological properties has brought great attention to rare-earth monopnictides semimetals. For some of them, like LaSb, it is unclear whether they show nontrivial topology or not based on density functional theory calculations and angular resolved photoemission spectroscopy measurements. Here we use hybrid density functional theory to demonstrate that LaSb is in fact a trivial topological semimetal, in agreement with experiments, but on the verge of a transition to a topological phase. In this work, we show that under compressive epitaxial strain, the La $\textit{d}$ band crosses the Sb $\textit{p}$ band near the $\textit{Z}$ point in the Brillouin zone, stabilizing a topologically nontrivial phase, opening unique opportunities to probe the inter-relation between magnetotransport properties and the effects of band topology by examining epitaxially strained and unstrained thin films of the same material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Nature of native atomic defects in ZrTe 5 and their impact on the low-energy electronic structure

Over the past decades, investigations of the anomalous low-energy electronic properties of ZrTe 5 have reached a wide array of conclusions. An open question is the growth method's impact on the stoichiometry of ZrTe 5 samples, especially given the very small density of states near its chemical potential. In this work, we report on high-resolution scanning tunneling microscopy and spectroscopy measurements performed on samples grown via different methods. Using density functional theory calculations, we identify the most prevalent types of atomic defects on the surface of ZrTe 5 , namely, Te vacancies and intercalated Zr atoms. Finally, we precisely quantify their density and outline their role as ionized defects in the anomalous resistivity of this material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Ti-6Al-4V to over 1.2 TPa: Shock Hugoniot experiments, ab initio calculations, and a broad-range multiphase equation of state

Titanium alloys are used in a large array of applications. In this work we focus our attention on the most used alloy, Ti-6Al-4V (Ti64), which has excellent mechanical and biocompatibility properties with applications in aerospace, defense, biomedical, and other fields. Here we present high-fidelity experimental shock compression data measured on Sandia’s Z machine. We extend the principal shock Hugoniot for Ti64 to more than threefold compression, up to over 1.2 TPa. We use the data to validate our ab initio molecular dynamics simulations and to develop a highly reliable, multiphase equation of state (EOS) for Ti64, spanning a broad range of temperature and pressures. The first-principles simulations show very good agreement with Z data and with previous three-stage gas gun data from Sandia’s STAR facility. The resulting principal Hugoniot and the broad-range EOS and phase diagram up to 10 TPa and 10 5 K are suitable for use in shock experiments and in hydrodynamic simulations. The high-precision experimental results and high-fidelity simulations demonstrate that the Hugoniot of the Ti64 alloy is stiffer than that of pure Ti and reveal that Ti64 melts on the Hugoniot at a significantly lower pressure and temperature than previously modeled.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites

The dissociative adsorption of methanol was investigated on Cu(111) and ultrathin Cu 2 O films. We employed synchrotron-based Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Scanning Tunneling Microscopy (STM) to study the dynamics of gas–solid interactions, and calculations based on Density Functional Theory (DFT) were used to examine the reaction path. C 1s XPS spectra revealed that methanol underwent dissociative adsorption on plain Cu(111) to form methoxy (CH 3 O), formaldehyde (H 2 CO), and formate (HCOO) at a pressure range of 0.5–10 mTorr, with these species remaining on the surface after evacuation. This was accompanied by the appearance of a low coverage (~0.05 ML) of O ads in the O 1s which can be considered a highly active site for methanol activation. The high activity is apparent by a coverage of 0.8 ML of methoxy at room temperature. STM was unable to image these species at room temperature as they were highly mobile on metallic copper. In contrast, for CH 3 OH on Cu 2 O/Cu(111), STM showed clear hot spots for reaction and a complex array of adsorption structures. On the oxide substrate, there was decomposition of methanol to H 2 CO, CH 3 O, HCOO, and hydrocarbon species (CH x ) due to the subsequent interactions of methanol with lattice oxygen. Cu(111) remained entirely saturated with decomposition products under 10 mTorr of methanol (θ ≈ 0.97 ML), whereas the Cu 2 O overlayer was saturated at a much lower coverage (θ ≈ 0.30 ML). STM revealed rows and step edges of Cu 2 O decorated with decomposition products and metallic Cu islands ~5 nm in size. The difference in activity between Cu(111) and Cu 2 O/Cu(111) is attributed to the significant amount of O present on the oxide surface. Additionally, Density Functional theory (DFT) calculations described the XPS measurements well, showing a likely methanol dissociation to *CH 3 O and therefore a surface reduction. More importantly, the DFT results revealed that it was the chemisorbed oxygen on Cu 2 O/Cu(111) which oxidized the dissociated *CH 3 O to *HCOO and eventually CO 2 , while the reaction only involving upper oxygen on the Cu 2 O hexagonal ring led to the formation of H 2 CO.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Pressure-induced charge orders and their postulated coupling to magnetism in hexagonal multiferroic LuFe 2 O 4

Hexagonal LuFe 2 O 4 is a promising charge order (CO) driven multiferroic material with high charge and spin-ordering temperatures. The coexisting charge and spin orders on Fe 3+ /Fe 2+ sites result in magnetoelectric behaviors, but the coupling mechanism between the charge and spin orders remains elusive. Here, by tuning external pressure, we reveal three charge-ordered phases with suggested correlation to magnetic orders in LuFe 2 O 4 : (i) a centrosymmetric incommensurate three-dimensional CO with ferrimagnetism, (ii) a non-centrosymmetric incommensurate quasi-two-dimensional CO with ferrimagnetism, and (iii) a centrosymmetric commensurate CO with antiferromagnetism. Experimental in situ single-crystal X-ray diffraction and X-ray magnetic circular dichroism measurements combined with density functional theory calculations suggest that the charge density redistribution caused by pressure-induced compression in the frustrated double-layer [Fe 2 O 4 ] cluster is responsible for the correlated spin-charge phase transitions. The pressure-enhanced effective Coulomb interactions among Fe-Fe bonds drive the frustrated (1/3, 1/3) CO to a less frustrated (1/4, 1/4) CO, which induces the ferrimagnetic to antiferromagnetic transition. Our results not only elucidate the coupling mechanism among charge, spin, and lattice degrees of freedom in LuFe 2 O 4 , but also provide a new way to tune the spin-charge orders in a highly controlled manner.

36 MATERIALS SCIENCE↗