Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “variational principles”

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.

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

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Testing lepton flavor universality at future Z factories

As one of the hypothetical principles in the Standard Model (SM), lepton flavor universality (LFU) should be tested with a precision as high as possible such that the physics violating this principle can be fully examined. The run of a Z factory at a future e + e − collider, such as the Circular Electron-Positron Collider or Future Circular Collider (electron/positron), provides a great opportunity to perform this task because of the large statistics and high reconstruction efficiencies for b hadrons at the Z pole. In this paper, we present a systematic study on the LFU test in future Z factories. The goal is threefold. First, we study the sensitivities of measuring the LFU-violating observables of b → c τ ν , i.e., R J / ψ , R D s , R D s * , and R Λ c , where τ decays muonically. For this purpose, we develop the strategies for event reconstruction, based on the track information significantly. Second, we explore the sensitivity robustness against detector performance and its potential improvement with the message of event shape or beyond the b -hadron decays. A picture is drawn on the variation of analysis sensitivities with the detector tracking resolution and soft photon detectability, and the impact of Fox-Wolfram moments is studied on the measurement of relevant flavor events. Finally, we interpret the projected sensitivities in the SM effective field theory, by combining the LFU tests of b → c τ ν and the measurements of b → s τ + τ − and b → s ν ¯ ν . We show that the limits on the LFU-violating energy scale can be pushed up to ∼ O ( 10 ) TeV for ≲ O ( 1 ) Wilson coefficients at Tera- Z . Published by the American Physical Society 2024

Astronomy & Astrophysics↗
DOE OSTI2024

Strain-concentration for fast, compact photonic modulation and non-volatile memory

A critical figure of merit (FoM) for electro-optic (EO) modulators is the transmission change per voltage, d T / d V . Conventional approaches in wave-guided modulators maximize d T / d V via a high EO coefficient or longer light-material interaction lengths but are ultimately limited by material losses and nonlinearities. Optical and RF resonances improve d T / d V at the cost of spectral non-uniformity, especially for high- Q optical cavity resonances. Here, we introduce an EO modulator based on piezo-strain-concentration of a photonic crystal cavity to address both trade-offs: (i) it eliminates the trade-off between d T / d V and waveguide loss—i.e., enhancement of the resonance tuning efficiency d v c / d V for the fixed EO coefficient, waveguide length, and cavity Q —and (ii) at high DC strains it exhibits a non-volatile (NV) cavity tuning Δ v c ,NV for passive memory and programming of multiple devices into resonance despite fabrication variations. The device is fabricated on a scalable silicon nitride-on-aluminum nitride platform. We measure d v c / d V =177±1MHz/V, corresponding to Δ v c =40±0.32GHz for a voltage spanning ±120V with an energy consumption of δ U /Δ v c =0.17nW/GHz. The modulation bandwidth is flat up to ω BW,3dB /2 π =3.2±0.07MHz for broadband DC-AC and 142±17MHz for resonant operation near a 2.8 GHz mechanical resonance. Optical extinction up to 25 dB is obtained via Fano-type interference. Strain-induced beam-buckling modes are programmable under a “read-write” protocol with a continuous, repeatable tuning range of 5±0.25GHz, allowing for storage and retrieval, which we quantify with mutual information of 2.4 bits and a maximum non-volatile excursion of 8 GHz. Using a full piezo-optical finite-element-model (FEM) we identify key design principles for optimizing strain-based modulators and chart a path towards achieving performance comparable to lithium niobate-based modulators and the study of high strain physics on-chip.

Wen, Y. Henry (ORCID:0009000685423628)↗
DOE OSTI2022

Testing the Cosmological Principle: Astrometric Limits on Systemic Motion of Quasars at Different Cosmological Epochs

A sample of 60,410 bona fide optical quasars with astrometric proper motions in Gaia Early Data Release 3 and spectroscopic redshifts above 0.5 in an oval 8400 square degree area of the sky is constructed. Using orthogonal Zernike functions of polar coordinates, the proper motion fields are fitted in a weighted least-squares adjustment of the entire sample and of six equal bins of sorted redshifts. The overall fit with 37 Zernike functions reveals a statistically significant pattern, which is likely to be of instrumental origin. The main feature of this pattern is a chain of peaks and dips mostly in the R.A. component with an amplitude of 25 μ as yr -1 . This field is subtracted from each of the six analogous fits for quasars grouped by redshifts covering the range 0.5 through 7.03, with median values of 0.72, 1.00, 1.25, 1.52, 1.83, 2.34. The resulting residual patterns are noisier, with formal uncertainties up to 8 μ as yr -1 in the central part of the area. We detect a single high-confidence Zernike term for the R.A. proper motion components of quasars with redshifts around 1.52 representing a general gradient of 30 μ as yr -1 over 150° on the sky. We do not find any small- or medium-scale systemic variations of the residual proper motion field as functions of redshift above the 2.5 σ significance level.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.

25 ENERGY STORAGE↗
DOE OSTI2020

Many-body electronic structure of LaScO 3 by real-space quantum Monte Carlo

We present real space quantum Monte Carlo (QMC) calculations of the scandate LaSc0 3 that proved to be challenging for traditional electronic structure approaches due to strong correlation effects resulting in inaccurate band gaps from DFT and GW methods when compared with existing experimental data. Besides calculating an accurate QMC band gap corrected for supercell size biases and in agreement with numerous experiments, we also predict the cohesive energy of the crystal using the standard fixed-node QMC without any empirical or non-variational parameters. We show that promotion (optical) gap and fundamental gap agree with each other illustrating a clear absence of significant excitonic effects in the ideal crystal. We obtained these results in perfect consistency in two independent tracks that employ different basis sets (plane wave vs. localized gaussians), different codes for generating orbitals (QUANTUM ESPRESSO vs. CRYSTAL), different QMC codes (QMCPACK vs. QWALK) and different high-accuracy pseudopotentials (ccECPs vs. Troullier-Martins) presenting the maturity and consistency of QMC methodology and tools for studies of strongly correlated problems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Surrogate optimization of variational quantum circuits

Variational quantum eigensolvers are touted as a near-term algorithm capable of impacting many applications. However, the potential has not yet been realized, with few claims of quantum advantage and high resource estimates, especially due to the need for optimization in the presence of noise. Finding algorithms and methods to improve convergence is important to accelerate the capabilities of near-term hardware for VQE or more broad applications of hybrid methods in which optimization is required. To this goal, we look to use modern approaches developed in circuit simulations and stochastic classical optimization, which can be combined to form a surrogate optimization approach to quantum circuits. Using an approximate (classical CPU/GPU) state vector simulator as a surrogate model, we efficiently calculate an approximate Hessian, passed as an input for a quantum processing unit or exact circuit simulator. This method will lend itself well to parallelization across quantum processing units. We demonstrate the capabilities of such an approach with and without sampling noise and a proof-of-principle demonstration on a quantum processing unit utilizing 40 qubits.

Gustafson, Erik J. [RIACS, Mtn. View] (ORCID:00000↗
DOE OSTI2023

Genomic materials design: CALculation of PHAse Dynamics

The CALPHAD system of fundamental phase-level databases, now known as the Materials Genome, has enabled a mature technology of computational materials design and qualification that has already met the acceleration goals of the national Materials Genome Initiative. Here, as first commercialized by QuesTek Innovations, the methodology combines efficient genomic-level parametric design of new material composition and process specifications with multidisciplinary simulation-based forecasting of manufacturing variation, integrating efficient uncertainty management. Recent projects demonstrated under the multi-institutional CHiMaD Design Center notably include novel alloys designed specifically for additive manufacturing. With the proven success of the CALPHAD-based Materials Genome technology, current university research emphasizes new methodologies for affordable accelerated expansion of more accurate CALPHAD databases. Rapid adoption of these new capabilities by US apex corporations has compressed the materials design and development cycle to under 2 years, enabling a new “materials concurrency” integrated into a new level of concurrent engineering supporting an unprecedented level of manufacturing innovation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

RNA‐Seq analysis revealed the molecular mechanisms of photobiomodulation effect on human fibroblasts

Abstract Background The photobiomodulation (PBM) effect has been applied to various clinical therapy for a long time. However, the mechanism related to the PBM effect in terms of wavelengths has been lack of in‐depth study, except that ultraviolet radiation has attracted much attention due to its strong cell‐killing effect. Purpose To clarify the principle behind PBM and the main mechanism of improvement. Methods To carry on this study, we created light equipment using three LED chips, which emit 390 nm ultraviolet radiation, 415 nm blue light and 660 nm red light, respectively. We choose human fibroblasts (HF) to be irradiated by three different wavelengths for PBM test. In this study, we used cell counting kit (CCK‐8) test to show the cell proliferation roughly and reported on a systematic RNA sequencing (RNA‐seq) analysis at transcriptional expression levels from HF, which accepted PBM of different wavelengths of light. Results We found that 415 nm blue light inhibited cell proliferation and 660 nm red light stimulated cell proliferation while 390 nm ultraviolet radiation has little influence on cell proliferation. Furthermore, RNA‐seq results showed that CSF1R, PPP3CC, ITGAL, ITGAM, IL2RB, and several other differentially expressed genes (DEGs) are involved in the cell proliferation. Relative DEGs values for matrix metalloproteinases (MMPs) gene family have shown a great difference in blue and red light radiation especially on MMP25, MMP9, MMP21, and MMP13. Conclusion Taken together, the results provide a valuable resource to describe the variation of HFs under PBM of different light at gene level.

Li, Wenqi↗
DOE OSTI2020

Deep learning to generate in silico chemical property libraries and candidate molecules for small molecule identification in complex samples

Comprehensive and unambiguous identification of small molecules in complex samples will revolutionize our understanding of the role of metabolites in biological systems. Existing and emerging technologies have enabled measurement of chemical properties of molecules in complex mixtures and, in concert, are sensitive enough to resolve even stereoisomers. Despite these experimental advances, small molecule identification is inhibited by (i) chemical reference libraries (e.g. mass spectra, collision cross section, and other measurable property libraries) representing <1% of known molecules, limiting the number of possible identifications, and (ii) the lack of a method to generate candidate matches directly from experimental features (i.e. without a library). To this end, we developed a variational autoencoder (VAE) to learn a continuous numerical, or latent, representation of molecular structure to expand reference libraries for small molecule identification. We extended the VAE to include a chemical property decoder, trained as a multitask network, in order to shape the latent representation such that it assembles according to desired chemical properties. The approach is unique in its application to metabolomics and small molecule identification, with its focus on properties that can be obtained from experimental measurements (m/z, CCS) paired with its training paradigm, which involved a cascade of transfer learning iterations. First, molecular representation is learned from a large dataset of structures with m/z labels. Next, in silico property values are used to continue training, as experimental property data is limited. Finally, the network is further refined by being trained with the experimental data. This allows the network to learn as much as possible at each stage, enabling success with progressively smaller datasets without overfitting. Once trained, the network can be used to predict chemical properties directly from structure, as well as generate candidate structures with desired chemical properties. Our approach is orders of magnitude faster than first-principles simulation for CCS property prediction. Additionally, the ability to generate novel molecules along manifolds, defined by chemical property analogues, positions DarkChem as highly useful in a number of application areas, including metabolomics and small molecule identification, drug discovery and design, chemical forensics, and beyond.

Colby, Sean M.↗
DOE OSTI2021

Certification of Uranium Isotope Amount Ratios in a Suite of Uranium Ore Concentrate Certified Reference Materials

Here, in this study, data from thirteen laboratories from around the world are presented for a successful certification of uranium isotope ratios in uranium ore concentrate (UOC) certified reference materials from the National Research Council Canada. Different mass spectrometric measurement principles (including SF-ICP-MS, quadruple ICP-MS, TIMS, MC-ICP-MS, SIMS and AMS) and measurement procedures were employed. In general, data from all sources exhibit good consistency with TIMS and MC-ICP-MS showing superior performance. The three candidate UOC CRMs (UCLO-1, UCHI-1 and UPER-1) have natural uranium isotope ratios with certified values of 0.5304(7) x 10 -4 , 0.5475(2) x 10 -4 and 0.5361(4) x 10 -4 for n( 234 U)/n( 238 U) and 0.007 2563(13), 0.007 2563(10) and 0.007 2542(11) for n( 235 U)/n( 238 U), respectively, with expanded uncertainty (k = 2) applicable to the last digit of the value given in the parentheses. Information values for n( 236 U)/n( 238 U) in these three CRMs, measured by AMS, are also provided: 10 x 10 -12 , 200 x 10 -12 and 22 x 10 -12 . The uncertainties of the proposed certified values of uranium isotope ratios in UOC CRMs are superior to available reference materials, and the values of n( 234 U)/n( 238 U) and n( 236 U)/n( 238 U) show significant variation among the three CRMs.

58 GEOSCIENCES↗
DOE OSTI2021

Determining fast-S and slow-S propagation directions with SV-P data produced by buried explosives and recorded with vertical geophones

We have evaluated the concept of practicing S-wave reflection seismology with legacy 3D seismic data generated by a P-wave source and recorded with only vertical geophones. This type of S-wave imaging is based on the principle that seismic P-wave sources not only produce a downgoing illuminating P wavefield, but they also simultaneously produce a downgoing illuminating SV wavefield that, in almost all cases, is suitable for S-wave reflection imaging. The S-mode used in this study is the SV-P, or converted-P, mode. This mode involves a downgoing illuminating SV wavefield and an upgoing reflected P-mode that is recorded by vertical geophones. In flat-layered stratigraphy, the lengths of the SV and P raypaths in SV-P imaging are identical to the lengths of the SV and P raypaths in P-SV imaging with P-sources and 3C geophones. P-SV imaging of deep rocks has been practiced for more than two decades; SV-P imaging is a new concept. SV-P data should provide the same options for investigating deep rocks as do P-SV data. We have determined one of the equivalences between SV-P data extracted from vertical-geophone data and P-SV data extracted from horizontal geophones: that both modes react to azimuth-dependent variations in the S velocity in anisotropic rocks. Azimuthal variations in the SV-P traveltime can be used to define the polarization direction of the fast-S-wave mode, which is also the azimuth of the maximum horizontal stress (SHmax). Our investigation demonstrates a noninvasive method for monitoring changes in the SHmax azimuth across a CO 2 storage reservoir, or any targeted porous rock, as fluids are cycled into, and then out of, that rock’s pore space.

Geochemistry & Geophysics↗
DOE OSTI2021

Entanglement rearrangement in self-consistent nuclear structure calculations

Background: Entanglement plays a central role in a diverse array of increasingly important research areas, including quantum computation, simulation, measurement, sensing, and communication. Extensive suites of investigations have been performed to better understand entanglement in atomic and molecular quantum many-body systems, while the exploration of entanglement in the structure of nuclei and their reactions is presently in its infancy. Purpose: The goal of this work is to begin investigating the entanglement properties of nuclei from first-principles nuclear many-body calculations. We attempt to identify common features and emergent structures of entanglement that could ultimately lead to new and natural many-body schemes. With an eye toward quantum accelerators in future hybrid-supercomputers, criteria for partitioning nuclear many-body calculations into quantum and classical components may provide advantages in future large-scale computations. Along the way we look for explanations of the relative success of phenomenological models such as the nuclear shell model, and for better ways to match to low-energy nuclear effective field theories and lattice QCD calculations to nuclear many-body techniques that are based upon entanglement. Method: We explore the entanglement between single-particle states in 4 He and 6 He. The patterns of entanglement emerging from different single-particle bases are compared, and possible links with the convergence of observables are explored, in particular, ground-state energies. The nuclear wave functions are obtained by performing active-space no-core configuration-interaction calculations using a two-body nucleon-nucleon interaction derived from chiral effective field theory. Entanglement measures within single-particle bases exhibiting different degrees of complexity are determined, in particular, harmonic oscillator (HO), Hartree-Fock (HF), natural (NAT) and variational natural (VNAT) bases. Specifically, single-orbital entanglement entropy, two-orbital mutual information, and negativity are studied. Results: The entanglement structures in 4 He and 6 He are found to be more localized within NAT and VNAT bases than within a HO basis for the optimal HO parameters we have worked with. In particular a core-valence structure clearly emerges from the full no-core calculation of 6 He. Here, the two-nucleon mutual information shows that the VNAT basis, which typically exhibits good convergence properties, effectively decouples the active and inactive spaces. Conclusions: Measures of one- and two-nucleon entanglement are found to be useful in analyzing the structure of nuclear wave functions, in particular the efficacy of basis states, and may provide useful metrics toward developing more efficient schemes for ab initio computations of the structure and reactions of nuclei, and quantum many-body systems more generally.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Shell-model studies of the astrophysical r p -process reactions S 34 ( p , γ ) Cl 35 and Cl 34 g , m ( p , γ ) Ar 35

Background: Dust grains condensed in the outflows of presolar classical novae should have been present in the protosolar nebula. Candidates for such presolar nova grains have been found in primitive meteorites and can in principle be identified by their isotopic ratios, but the ratios predicted by state-of-the-art one-dimensional hydrodynamic models are uncertain due to nuclear-physics uncertainties. Purpose: To theoretically calculate the thermonuclear rates and uncertainties of the S 34 ( p , γ ) Cl 35 and Cl 34 g , m ( p , γ ) Ar 35 reactions and investigate their impacts on the predicted 34 S/ 32 S isotopic ratio for presolar nova grains. Method: A shell-model approach in a (0 +1 ) ℏ ω model space was used to calculate the properties of resonances in the 34 S(p ,γ ) 35 Cl and 34 g,m Cl (p ,γ ) 35 Ar reactions and their thermonuclear rates. Uncertainties were estimated using a Monte Carlo method. The implications of these rates and their uncertainties on sulfur isotopic nova yields were investigated using a postprocessing nucleosynthesis code. The rates for transitions from the ground state of 34 Cl as well as from the isomeric first excited state of 34 Cl were explicitly calculated. Results: At energies in the resonance region near the proton-emission threshold, many negative-parity states appear. Energies, spectroscopic factors, and proton-decay widths are reported. The resulting thermonuclear rates are compared with previous determinations. Conclusions: The shell-model calculations alone are sufficient to constrain the variation of the 34 S/ 32 S ratios to within about 30%. Uncertainties associated with other reactions must also be considered, but in general we find that the 34 S/ 32 S ratios are not a robust diagnostic to clearly identify presolar grains made from nova ejecta.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Design principles of tandem cascade photoelectrochemical devices

Cascade photoelectrocatalysis (PEC) is a possible method to improve the selectivity of solar-driven CO 2 reduction (CO 2 R). This concept can be realized by coupling different CO 2 R catalysts to different subcells in a multijunction photovoltaic (PV) stack. Efficient implementation will require careful tuning of the photocurrents and design of the photovoltages provided by the subcells to the CO 2 R catalysts in such a way as to facilitate the target reaction. Here, we outline the design principles of the tandem PEC approach using two-step conversion of CO 2 to ethylene in aqueous electrolyte, via a CO intermediate, as a model system. To perform this reaction, the first coupled PV-catalyst component should provide 4 electrons to reduce 2 molecules of CO 2 to CO; the second component should provide 8 electrons to reduce 2 CO molecules to C 2 H 4 . Based on known CO 2 R catalysts, the overpotential required to produce CO can be less than that required to reduce it to ethylene, creating the opportunity for improved efficiency. Cascade PEC can be realized in a three-terminal tandem (3TT) configuration using III–V-semiconductor based subcells coupled to Au (produces CO intermediate) and Cu (converts CO to ethylene). The current to each catalyst can be controlled by the area of the subcell exposed to the electrolyte, and the photovoltage is determined by the materials selected and device configuration. Operating conditions are found by simulating the coupled system using the open-source circuit simulator SPICE (Simulation Program with Integrated Circuits Emphasis). We identify conditions under which a 3TT configuration can have a higher solar to chemical conversion efficiency compared to a two-terminal two-junction tandem (2T 2J) with the same absorbers and a Cu catalyst only. We also show that 3TT PEC devices can be less sensitive to variations in catalyst activity compared to 2T devices. Lastly, we discuss the applications of cascade PEC to CO 2 reduction, using different intermediates, and to other chemical networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Variation of carrier density in semimetals via short-range correlation: A case study with nickelate NdNiO 2

Carrier density is one of the key controlling factors of material properties, particularly in controlling the essential correlations in strongly correlated materials. Typically, carrier density is externally tuned by doping or gating and remains fixed below room temperature. Strangely, the carrier density in correlated semimetals is often found to vary sensitively against weak external controls such as temperature, magnetic field, and pressure. Here, we develop a realistic simulation scheme that incorporates interatomic noncollinear magnetic correlation without a long-range order. Using the recently discovered nickelate superconductor as an example, we demonstrate a rather generic low-energy mechanism that in semimetals short-range correlation can reversely modulate the carrier density as well. Such a mutual influence between correlation and carrier density provides an extra ingredient for sensitive bifurcating behavior. This special feature of correlated semimetals explains their versatile carrier density at low energy and opens up new possibilities of functionalizing these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Mirror symmetry breaking and lateral stacking shifts in twisted trilayer graphene

Here, we construct a continuum model of twisted trilayer graphene using ab initio density-functional-theory calculations, and we apply it to address twisted trilayer electronic structure. Our model accounts for moiré variation in site energies, hopping between outside layers, and hopping within layers. We focus on the role of a mirror symmetry present in ABA graphene trilayers with a middle layer twist. The mirror symmetry is lost intentionally when a displacement field is applied between layers, and unintentionally when the top layer is shifted laterally relative to the bottom layer. We calculate two band-structure characteristics that are directly relevant to transport measurements, namely the Drude weight and the weak-field Hall conductivity. We relate them via the Hall density to assess the influence of the accidental lateral stacking shifts currently present in all experimental devices on electronic properties. Finally, we comment on the role of the possible importance of accidental lateral stacking shifts for superconductivity in twisted trilayers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Spectral-partitioned Kohn-Sham density functional theory

Here we introduce a general, variational scheme for systematic approximation of a given Kohn-Sham free-energy functional by partitioning the density matrix into distinct spectral domains, each of which may be spanned by an independent diagonal representation without requirement of mutual orthogonality. It is shown that by generalizing the entropic contribution to the free energy to allow for independent representations in each spectral domain, the free energy becomes an upper bound to the exact (unpartitioned) Kohn-Sham free energy, attaining this limit as the representations approach Kohn-Sham eigenfunctions. A numerical procedure is devised for calculation of the generalized entropy associated with spectral partitioning of the density matrix. The result is a powerful framework for Kohn-Sham calculations of systems whose occupied subspaces span multiple energy regimes. As a case in point, we apply the proposed framework to warm- and hot-dense matter described by finite-temperature density functional theory, where at high energies the density matrix is represented by that of the free-electron gas, while at low energies it is variationally optimized. We derive expressions for the spectral-partitioned Kohn-Sham Hamiltonian, atomic forces, and macroscopic stresses within the projector-augmented wave (PAW) and the norm-conserving pseudopotential methods. It is demonstrated that at high temperatures, spectral partitioning facilitates accurate calculations at dramatically reduced computational cost. Moreover, as temperature is increased, fewer exact Kohn-Sham states are required for a given accuracy, leading to further reductions in computational cost. Finally, it is shown that standard multiprojector expansions of electronic orbitals within atomic spheres in the PAW method lack sufficient completeness at high temperatures. Spectral partitioning provides a systematic solution for this fundamental problem.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Starting-point-independent quantum Monte Carlo calculations of iron oxide

Quantum Monte Carlo (QMC) methods are useful for studies of strongly correlated materials because they are many body in nature and use the physical Hamiltonian. Typical calculations assume as a starting point a wave function constructed from single-particle orbitals obtained from one-body methods, e.g., density functional theory. However, mean-field-derived wave functions can sometimes lead to systematic QMC biases if the mean-field result poorly describes the true ground state. In this study, we examine the accuracy and flexibility of QMC trial wave functions using variational and fixed-node diffusion QMC estimates of the total spin density and lattice distortion of antiferromagnetic iron oxide (FeO) in the ground state B1 crystal structure. We found that for relatively simple wave functions the predicted lattice distortion was controlled by the choice of single-particle orbitals used to construct the wave function, rather than by subsequent wave function optimization techniques within QMC. By optimizing the orbitals with QMC, we then demonstrate starting-point independence of the trial wave function with respect to the method by which the orbitals were constructed by demonstrating convergence of the energy, spin density, and predicted lattice distortion for two qualitatively different sets of orbitals. The results suggest that orbital optimization is a promising method for accurate many-body calculations of strongly correlated condensed phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗