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DOE OSTI2026

An Anisotropic Yield and Damage Material Model to Improve the Contact Pressure Analysis in a Biomass Shredding System

Size reduction systems used in biomass processing break biomass into smaller pieces by utilizing the kinetic energy from the sharp rotating blades. Abrasive and/or erosive wear caused by biomass comminution results in blade wear of the sharp edged cutters, deteriorating the process efficiency. Here, this study aims to optimize the blade design and improve the system efficiency by attempting to understand the interactions between the blades and biomass particles. Since real-time monitoring of these interactions is impractical during operation, mechanical simulations offer a viable alternative for investigating the shredding process. Yet, the irregular geometry and complex mechanical properties of biomass—such as the anisotropic nature of woodchips and their nonlinear fracture behavior—pose significant challenges for accurately simulating contact pressure. In this work an anisotropic yield material model, along with a damage initiation and evolution function, is applied to the woodchip particle to study the contact pressure on shredder blade, offering a scientific basis for improved blade design and process efficiency. This approach can be extended to other biomass processing systems with similar anisotropic feedstocks, making it a valuable tool for advancing sustainable biomass utilization.

09 - BIOMASS FUELS↗

DOE OSTI2017

Evolution of the Reactor Antineutrino Flux and Spectrum at Daya Bay

Here, the Daya Bay experiment has observed correlations between reactor core fuel evolution and changes in the reactor antineutrino flux and energy spectrum. Four antineutrino detectors in two experimental halls were used to identify 2.2 million inverse beta decays (IBDs) over 1230 days spanning multiple fuel cycles for each of six 2.9 GW th reactor cores at the Daya Bay and Ling Ao nuclear power plants. Using detector data spanning effective 239 Pu fission fractions F 239 from 0.25 to 0.35, Daya Bay measures an average IBD yield ¯σf of (5.90±0.13)×10 –43 cm 2 /fission and a fuel-dependent variation in the IBD yield, dσ f /dF 239 , of (–1.86±0.18)×10 –43 cm 2 /fission. This observation rejects the hypothesis of a constant antineutrino flux as a function of the 239 Pu fission fraction at 10 standard deviations. The variation in IBD yield is found to be energy dependent, rejecting the hypothesis of a constant antineutrino energy spectrum at 5.1 standard deviations. While measurements of the evolution in the IBD spectrum show general agreement with predictions from recent reactor models, the measured evolution in total IBD yield disagrees with recent predictions at 3.1σ. This discrepancy indicates that an overall deficit in the measured flux with respect to predictions does not result from equal fractional deficits from the primary fission isotopes 235 U, 239 Pu, 238 U, and 241 Pu. Based on measured IBD yield variations, yields of (6.17±0.17) and (4.27±0.26)×10 –43 cm 2 /fission have been determined for the two dominant fission parent isotopes 235 U and 239 Pu. A 7.8% discrepancy between the observed and predicted 235 U yields suggests that this isotope may be the primary contributor to the reactor antineutrino anomaly.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

NASA NTRS1992

Secondary electron yields of solar system ices

The secondary electron yields of H2O, CO2, NH3, and CH3OH ices have been measured as a function of electron beam energy in the 2- to 30-keV energy range. The ices were produced on a liquid-nitrogen-cooled cold finger and transferred under vacuum to a SEM where the yield measurements were made. The imaging capabilities of the SEM provide a means of correlating the yield measurements with the morphology of the ices and are also used to monitor charging effects. The yields were determined by measuring the amplified current from a secondary electron detector and calibrating this current signal with the amplified current signal from samples of metals with known secondary electron yields. Each of the measured yields is found to decrease with an increase in energy in the 2- to 30-keV range. Estimates are given for the maximum secondary electron yield Y(max) of each ice and the energy at which this maximum yield occurs. Implications for the charging of solar system ice grains are discussed.

Suszcynsky, David M.↗

DOE OSTI2023

Molecular-Dynamics Analysis of the Mechanical Behavior of Plasma-Facing Tungsten

We report a systematic computational analysis of the mechanical behavior of plasma-facing component (PFC) tungsten focusing on the impact of void and helium (He) bubble defects on the mechanical response beyond the elastic regime. Specifically, we explore the effects of porosity and He atomic fraction on the mechanical properties and structural response of PFC tungsten, at varying temperature and bubble size. We find that the Young modulus of defective tungsten undergoes substantial softening that follows an exponential scaling relation as a function of matrix porosity and He atomic content. Beyond the elastic regime, our high strain rate simulations reveal that the presence of nanoscale spherical defects (empty voids and He bubbles) reduces the yield strength of tungsten in a monotonically decreasing fashion, obeying an exponential scaling relation as a function of tungsten matrix porosity and He concentration. Our detailed analysis of the structural response of PFC tungsten near the yield point reveals that yielding is initiated by emission of dislocation loops from bubble/matrix interfaces, mainly 1/2<111> shear loops, followed by gliding and growth of these loops and reactions to form <100> dislocations. Furthermore, dislocation gliding on the <111>{211} twin systems nucleates 1/6<111> twin regions in the tungsten matrix. These dynamical processes reduce the stress in the matrix substantially. Subsequent dislocation interactions and depletion of the twin phases via nucleation and propagation of detwinning partials lead the tungsten matrix to a next deformation stage characterized by stress increase during applied straining. Furthermore, our structural analysis reveals that the depletion of twin boundaries (areal defects) is strongly impacted by the density of He bubbles at higher porosities. After the initial stress relief upon yielding, increase in the dislocation density in conjunction with decrease in the areal defect density facilitates the initiation of dislocation-driven deformation mechanisms in the PFC crystal.

36 MATERIALS SCIENCE↗

DOE OSTI2017

H{sub 2} X{sup 1}Σ{sub g}{sup +}−c{sup 3}Π{sub u} Excitation by Electron Impact: Energies, Spectra, Emission Yields, Cross-sections, and H(1s) Kinetic Energy Distributions

The c{sup 3}Π{sub u} state of the hydrogen molecule has the second largest triplet-state excitation cross-section, and plays an important role in the heating of the upper thermospheres of outer planets by electron excitation. Precise energies of the H{sub 2}, D{sub 2}, and HD c{sup 3}Π{sub u}{sup −}(v,N) levels are calculated from highly accurate ab initio potential energy curves that include relativistic, radiative, and empirical non-adiabatic corrections. The emission yields are determined from predissociation rates and refined radiative transition probabilities. The excitation function and excitation cross-section of the c{sup 3}Π{sub u} state are extracted from previous theoretical calculations and experimental measurements. The emission cross-section is determined from the calculated emission yield and the extracted excitation cross-section. The kinetic energy (E {sub k}) distributions of H atoms produced via the predissociation of the c{sup 3}Π{sub u} state, the c{sup 3}Π{sub u}{sup −} – b{sup 3}Σ{sub u}{sup +} dissociative emission by the magnetic dipole and electric quadrupole, and the c{sup 3}Π{sub u} – a{sup 3}Σ{sub g}{sup +} – b{sup 3}Σ{sub u}{sup +} cascade dissociative emission by the electric dipole are obtained. The predissociation of the c{sup 3}Π{sub u}{sup +} and c{sup 3}Π{sub u}{sup −} states both produce H(1s) atoms with an average E {sub k} of ∼4.1 eV/atom, while the c{sup 3}Π{sub u}{sup −} – b{sup 3}Σ{sub u}{sup +} dissociative emissions by the magnetic dipole and electric quadrupole give an average E {sub k} of ∼1.0 and ∼0.8 eV/atom, respectively. The c{sup 3}Π{sub u} – a{sup 3}Σ{sub g}{sup +} – b{sup 3}Σ{sub u}{sup +} cascade and dissociative emission gives an average E {sub k} of ∼1.3 eV/atom. On average, each H{sub 2} excited to the c{sup 3}Π{sub u} state in an H{sub 2}-dominated atmosphere deposits ∼7.1 eV into the atmosphere while each H{sub 2} directly excited to the a{sup 3}Σ{sub g}{sup +} and d{sup 3}Π{sub u} states contribute ∼2.3 and ∼3.3 eV, respectively, to the atmosphere. The spectral distribution of the calculated continuum emission arising from the X{sup 1}Σ{sub g}{sup +} – c{sup 3}Π{sub u} excitation is significantly different from that of direct a{sup 3}Σ{sub g}{sup +} or d{sup 3}Π{sub u} excitations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Robustness of cement-based materials: From dosage variations to yield stress fluctuations

The idea behind the present work is to assess robustness of fresh cement-based materials (i.e. their ability to display the same properties when submitted to variations in the way they are produced) from a generic and analytical point of view. First, analytical models from literature relating components proportions and yield stress are combined into a multi-scale and physical approach and compared to our experimental yield stress measurements. In the second part, the derivation of these analytical relationships is used to assess robustness as a function of components proportions, which allows for the most sensitive variations to be mapped onto component dosage from a yield stress point of view. In the case of fluid concretes, this approach showcases the interest of working at slightly higher water content and slightly lower aggregates fraction along with benefits of viscosity modifying agents / plasticizers combination.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Distinguishing erbium dopants in Y 2 O 3 by site symmetry: Ab initio theory of two spin-photon interfaces

Here, we present a first-principles study of the defect formation and electronic structure of erbium (Er)–doped yttria (Y 2 O 3 ). This is an emerging material for spin-photon interfaces in quantum information science due to the narrow-linewidth optical emission from Er dopants at standard telecommunication wavelengths and their potential for quantum memories and transducers. We calculate formation energies of neutral and negatively and positively charged Er dopants and find the charge-neutral configuration to be the most stable, consistent with experiment. Of the two substitutional sites of Er for Y, the C 2 (more relevant for quantum memories) and C 3i (more relevant for quantum transduction), we identify the former as possessing the lowest formation energy. The electronic properties are calculated using the Perdew-Burke-Ernzerhof functional along with the Hubbard U parameter and spin-orbit coupling, which yields a ~ 6 μ B orbital and a ~ 3 μ B spin magnetic moment, and 11 electrons in the Er 4 f shell, confirming the formation of charge-neutral Er 3+ . This standard density functional theory approach underestimates the band gap of the host and lacks a first-principles justification for U . To overcome these issues we performed screened hybrid functional calculations, including a negative U for the 4 f orbitals, with mixing (α) and screening (w) parameters. These produced robust electronic features with slight modifications in the band gap and the 4 f splittings depending on the choice of tuning parameters. We also computed the many-particle electronic excitation energies and compared them with experimental values from photoluminescence.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Metal Sulfide Ion Exchangers: High Acid Stability of Na 2 x Mg 2 y – x Sn 4– y S 8 (NMS) and Topotactic Conversion to 2D Solid Acids with Semiconducting Character

Metal sulfide ion exchange materials (MSIEs) are of interest for nuclear waste remediation applications. Here, we report the high stability of two structurally related metal sulfide ion exchange materials, Na 2x Mg 2y–x Sn 4–y S 8 (Mg-NMS) and Na 2 SnS 3 (Na-NMS), in strongly acid media, in addition to the preparation of Na 2x Ni 2y–x Sn 4–y S 8 (Ni-NMS). Their formation progress during synthesis is studied with in-situ methods, with the target phases appearing in <15 min, reaction completion in <12 h, and high yields (75–80%). Upon contact with nitric or hydrochloric acid, these materials topotactically exchange Na + for H + , proceeding in a stepwise protonation pathway for Na 5.33 Sn 2.67 S 8 . Na-NMS is stable in 2 M HNO 3 and Mg-NMS is stable in 4 M HNO 3 for up to 4 h, while both NMS materials are stable in 6 M HCl for up to 4 days. However, the treatment of Mg-NMS and Na-NMS with 2–6 M H 2 SO 4 reveals a much slower protonation process since after 4 h of contact both NMS and HMS are present in the solution. The resultant protonated materials, H 2x Mg 2y–x Sn 4–y S 8 and H 4x [(H y Na y–1 ) 1.33x Sn 4––1.33x ]S 8 , are themselves solid acids and readily react with and intercalate a variety of organic amines, where the band gap of the resultant adduct is influenced by amine choice and can be tuned within the range of 1.88(5)–2.27(5) eV. The work function energy values for all materials were extracted from photoemission yield spectroscopy in air (PYSA) measurements and range from 5.47 (2) to 5.76 (2) eV, and the relative band alignments of the materials are discussed. DFT calculations suggest that the electronic structure of Na 2 MgSn 3 S 8 and H 2 MgSn 3 S 8 makes them indirect gap semiconductors with multi-valley band edges, with carriers confined to the [MgSn 3 S 8 ] 2– layers. Light electron effective masses indicate high electron mobilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Cells and methods for producing fatty alcohols

Recombinant cells and methods for improved yield of fatty alcohols. The recombinant cells harbor a recombinant thioesterase gene, a recombinant acyl-CoA synthetase gene, and a recombinant acyl-CoA reductase gene. In addition, a gene product from one or more of an acyl-CoA dehydrogenase gene, an enoyl-CoA hydratase gene, a 3-hydroxyacyl-CoA dehydrogenase gene, and a 3-ketoacyl-CoA thiolase gene in the recombinant cells is functionally deleted. Culturing the recombinant cells produces fatty alcohols at high yields.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2016

Measurement of a redshift-space power spectrum for BOSS galaxies and the growth rate at redshift 0.57

We present a measurement of the two-dimensional (2D) redshift-space power spectrum for the Baryon Oscillation Spectroscopic Survey Data Release 11 CMASS galaxies in the northern Galactic cap based on the method developed by Jing and Börner. In this method, we first measure the 2D redshift-space correlation function and obtain the 2D power spectrum based on Fourier transform of the correlation function. The method is tested with an N-body mock galaxy catalog, which demonstrates that the method can yield an accurate and unbiased measurement of the redshift-space power spectrum given that the input 2D correlation function is correct. Compared with previous measurements in literature that are usually based on direct Fourier transform in redshift space, our method has the advantages that the window function and shot noise are fully corrected. Thus, our measurement can facilitate a direct comparison with the theoretical predictions. Our 2D power spectrum, by construction, can reproduce the 2D correlation function, and it can reproduce, for example, the 2D power spectrum of Beutler et al. accurately if ours is convolved with the window function they provided. We then develop a method to measure the structure growth rate, by separating the anisotropic redshift-space power spectrum from the isotropic real-space power spectrum. We have carefully corrected for the nonlinearities in the mapping from real space to redshift space, according to the theoretical model of Zhang et al. Finally, we obtain the measurement of structure growth rate f(z{sub eff})σ {sub 8}(z{sub eff}) = 0.438 ± 0.037 at the effective redshift z{sub eff} = 0.57. The result is useful for constraining cosmological parameters. The measurements of the 2D power spectrum will be released soon.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Measurement of single-diffractive dijet production in proton-proton collisions at $\sqrt{s} =$ 8 TeV with the CMS and TOTEM experiments

Measurements are presented of the single-diffractive dijet cross section and the diffractive cross section as a function of the proton fractional momentum loss $\xi $ and the four-momentum transfer squared t. Both processes ${\text{ p }{}{}} {\text{ p }{}{}} \rightarrow {\text{ p }{}{}} {\text{ X }} $ and ${\text{ p }{}{}} {\text{ p }{}{}} \rightarrow {\text{ X }} {\text{ p }{}{}} $, i.e. with the proton scattering to either side of the interaction point, are measured, where ${\text{ X }} $ includes at least two jets; the results of the two processes are averaged. The analyses are based on data collected simultaneously with the CMS and TOTEM detectors at the LHC in proton–proton collisions at $\sqrt{s} = 8\,\text {Te}\text {V} $ during a dedicated run with $\beta ^{*} = 90\,\text {m} $ at low instantaneous luminosity and correspond to an integrated luminosity of $37.5{\,\text {nb}^{-1}} $. The single-diffractive dijet cross section $\sigma ^{{\text{ p }{}{}} {\text{ X }}}_{\mathrm {jj}}$, in the kinematic region $\xi < 0.1$, $0.03< |t | < 1\,\text {Ge}\text {V} ^2$, with at least two jets with transverse momentum $p_{\mathrm {T}} > 40\,\text {Ge}\text {V} $, and pseudorapidity $|\eta | < 4.4$, is $21.7 \pm 0.9\,\text {(stat)} \,^{+3.0}_{-3.3}\,\text {(syst)} \pm 0.9\,\text {(lumi)} \,\text {nb} $. The ratio of the single-diffractive to inclusive dijet yields, normalised per unit of $\xi $, is presented as a function of x, the longitudinal momentum fraction of the proton carried by the struck parton. The ratio in the kinematic region defined above, for x values in the range $-2.9 \le \log _{10} x \le -1.6$, is $R = (\sigma ^{{\text{ p }{}{}} {\text{ X }}}_{\mathrm {jj}}/\Delta \xi )/\sigma _{\mathrm {jj}} = 0.025 \pm 0.001\,\text {(stat)} \pm 0.003\,\text {(syst)} $, where $\sigma ^{{\text{ p }{}{}} {\text{ X }}}_{\mathrm {jj}}$ and $\sigma _{\mathrm {jj}}$ are the single-diffractive and inclusive dijet cross sections, respectively. The results are compared with predictions from models of diffractive and nondiffractive interactions. Monte Carlo predictions based on the HERA diffractive parton distribution functions agree well with the data when corrected for the effect of soft rescattering between the spectator partons.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2015

Pressure-induced emergence of unusually high-frequency transverse excitations in a liquid alkali metal: Evidence of two types of collective excitations contributing to the transverse dynamics at high pressures

Unlike phonons in crystals, the collective excitations in liquids cannot be treated as propagation of harmonic displacements of atoms around stable local energy minima. The viscoelasticity of liquids, reflected in transition from the adiabatic to elastic high-frequency speed of sound and in absence of the long-wavelength transverse excitations, results in dispersions of longitudinal (L) and transverse (T) collective excitations essentially different from the typical phonon ones. Practically, nothing is known about the effect of high pressure on the dispersion of collective excitations in liquids, which causes strong changes in liquid structure. Here dispersions of L and T collective excitations in liquid Li in the range of pressures up to 186 GPa were studied by ab initio simulations. Two methodologies for dispersion calculations were used: direct estimation from the peak positions of the L/T current spectral functions and simulation-based calculations of wavenumber-dependent collective eigenmodes. It is found that at ambient pressure, the longitudinal and transverse dynamics are well separated, while at high pressures, the transverse current spectral functions, density of vibrational states, and dispersions of collective excitations yield evidence of two types of propagating modes that contribute strongly to transverse dynamics. Emergence of the unusually high-frequency transverse modes gives evidence of the breakdown of a regular viscoelastic theory of transverse dynamics, which is based on coupling of a single transverse propagating mode with shear relaxation. The explanation of the observed high-frequency shift above the viscoelastic value is given by the presence of another branch of collective excitations. With the pressure increasing, coupling between the two types of collective excitations is rationalized within a proposed extended viscoelastic model of transverse dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2014

A Radiation Chemistry Code Based on the Greens Functions of the Diffusion Equation

Ionizing radiation produces several radiolytic species such as.OH, e-aq, and H. when interacting with biological matter. Following their creation, radiolytic species diffuse and chemically react with biological molecules such as DNA. Despite years of research, many questions on the DNA damage by ionizing radiation remains, notably on the indirect effect, i.e. the damage resulting from the reactions of the radiolytic species with DNA. To simulate DNA damage by ionizing radiation, we are developing a step-by-step radiation chemistry code that is based on the Green's functions of the diffusion equation (GFDE), which is able to follow the trajectories of all particles and their reactions with time. In the recent years, simulations based on the GFDE have been used extensively in biochemistry, notably to simulate biochemical networks in time and space and are often used as the "gold standard" to validate diffusion-reaction theories. The exact GFDE for partially diffusion-controlled reactions is difficult to use because of its complex form. Therefore, the radial Green's function, which is much simpler, is often used. Hence, much effort has been devoted to the sampling of the radial Green's functions, for which we have developed a sampling algorithm This algorithm only yields the inter-particle distance vector length after a time step; the sampling of the deviation angle of the inter-particle vector is not taken into consideration. In this work, we show that the radial distribution is predicted by the exact radial Green's function. We also use a technique developed by Clifford et al. to generate the inter-particle vector deviation angles, knowing the inter-particle vector length before and after a time step. The results are compared with those predicted by the exact GFDE and by the analytical angular functions for free diffusion. This first step in the creation of the radiation chemistry code should help the understanding of the contribution of the indirect effect in the formation of DNA damage and double-strand breaks.

Plante, Ianik↗

DOE OSTI2019

Subleading power factorization with radiative functions

The study of amplitudes and cross sections in the soft and collinear limits allows for an understanding of their all orders behavior, and the identification of universal structures. At leading power soft emissions are eikonal, and described by Wilson lines. Beyond leading power the eikonal approximation breaks down, soft fermions must be added, and soft radiation resolves the nature of the energetic partons from which they were emitted. For both subleading power soft gluon and quark emissions, we use the soft collinear effective theory (SCET) to derive an all orders gauge invariant bare factorization, at both amplitude and cross section level. This yields universal multilocal matrix elements, which we refer to as radiative functions. These appear from subleading power Lagrangians inserted along the lightcone which dress the leading power Wilson lines. Here, the use of SCET enables us to determine the complete set of radiative functions that appear to O(λ 2 ) in the power expansion, to all orders in α s . For the particular case of event shape observables in e + e – → dijets we derive how the radiative functions contribute to the factorized cross section to O(λ 2 ).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2020

J/ψ production as a function of charged-particle multiplicity in p-Pb collisions at $ \sqrt{s_{\mathrm{NN}}} $ = 8.16 TeV

Inclusive J /ψ yields and average transverse momenta in p-Pb collisions at a center-of-mass energy per nucleon pair $ \sqrt{s_{\mathrm{NN}}} $ = 8 . 16 TeV are measured as a function of the charged-particle pseudorapidity density with ALICE. The J /ψ mesons are reconstructed at forward (2 . 03 < y cms < 3 . 53) and backward ( - 4 . 46 < y cms < - 2 . 96) center-of-mass rapidity in their dimuon decay channel while the charged-particle pseudorapidity density is measured around midrapidity. The J /ψ yields at forward and backward rapidity normalized to their respective average values increase with the normalized charged-particle pseudorapidity density, the former showing a weaker increase than the latter. The normalized average transverse momenta at forward and backward rapidity manifest a steady increase from low to high charged-particle pseudorapidity density with a saturation beyond the average value.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2018

Fermi-Löwdin orbital self-interaction correction to magnetic exchange couplings

We analyze the effect of removing self-interaction error on magnetic exchange couplings using the Fermi-Löwdin orbital self-interaction correction (FLOSIC) method in the framework of density functional theory (DFT). We compare magnetic exchange couplings obtained from self-interaction-free FLOSIC calculations with the local spin density approximation (LSDA) with several widely used DFT realizations and wave function based methods. To this end, we employ the linear H–He–H model system, six organic radical molecules, and [Cu 2 Cl 6 ] 2- as representatives of different types of magnetic interactions. Finally, we show that the simple self-interaction-free version of LSDA improves calculated couplings with respect to LSDA in all cases, even though the nature of the exchange interaction varies across the test set, and in most cases, it yields results comparable to modern hybrids and range-separated approximate functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Absorptive Hydrogen Scavenging for Enhanced Aromatics Yield During Non–oxidative Methane Dehydroaromatization on Mo/H–ZSM–5 Catalysts

Addition of Zr metal particles to MoC x /ZSM–5 in interpellet mixtures (2:1 weight ratio) resulted in maximum single–pass methane conversion of 27 % for dehydroaromatization at 973 K (in significant excess of the equilibrium prescribed circa 10 % conversion at these conditions) and a concurrent 1.4–5.6–fold increase in aromatic product yields due to circumvention of thermodynamic equilibrium limitations by absorptive H 2 removal by Zr while retaining cumulative aromatic product selectivity. Here, the absorptive function of the polyfunctional catalyst formulation can be regenerated by thermal treatment in He flow at 973 K, yielding above–equilibrium methane conversion in successive regeneration cycles. H 2 uptake experiments demonstrate formation of bulk ZrH 1.75 on hydrogen absorption by Zr at 973 K. Cooperation between absorption and catalytic centers distinct in location and function enables circumvention of persistent thermodynamic challenges in non–oxidative methane dehydrogenation.

03 NATURAL GAS↗

DOE OSTI2016

Cohesive energy and structural parameters of binary oxides of groups IIA and IIIB from diffusion quantum Monte Carlo

We have applied the diffusion quantum Monte Carlo (DMC) method to calculate the cohesive energy and the structural parameters of the binary oxides CaO, SrO, BaO, Sc{sub 2}O{sub 3}, Y{sub 2}O{sub 3}, and La{sub 2}O{sub 3}. The aim of our calculations is to systematically quantify the accuracy of the DMC method to study this type of metal oxides. The DMC results were compared with local, semi-local, and hybrid Density Functional Theory (DFT) approximations as well as with experimental measurements. The DMC method yields cohesive energies for these oxides with a mean absolute deviation from experimental measurements of 0.18(2) eV, while with local, semi-local, and hybrid DFT approximations, the deviation is 3.06, 0.94, and 1.23 eV, respectively. For lattice constants, the mean absolute deviations in DMC, local, semi-local, and hybrid DFT approximations are 0.017(1), 0.07, 0.05, and 0.04 Å, respectively. DMC is a highly accurate method, outperforming the DFT approximations in describing the cohesive energies and structural parameters of these binary oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗