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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Advances and Challenges of SCAN and r 2 SCAN Density Functionals in Transition‐Metal Compounds

ABSTRACT Transition‐metal compounds (TMCs) with open‐shell d ‐electrons are characterized by a complex interplay of lattice, charge, orbital, and spin degrees of freedom, giving rise to various fascinating applications. Often exhibiting exotic properties, these compounds are commonly classified as correlated systems due to strong inter‐electronic interactions called Hubbard U . This inherent complexity presents significant challenges to Kohn‐Sham density functional theory (KS‐DFT), the most widely used electronic structure method in condensed matter physics and materials science. While KS‐DFT is, in principle, exact for the ground‐state total energy, its exchange‐correlation energy must be approximated in practice. The mean‐field nature of KS implementations, combined with the limitations of current exchange‐correlation density functional approximations, has led to the perception that DFT is inadequate for correlated systems, particularly TMCs. Consequently, a common workaround involves augmenting DFT with an on‐site Hubbard‐like U correction. In recent years, the strongly constrained and appropriately normed (SCAN) density functional, along with its refined variant r 2 SCAN, has achieved remarkable progress in accurately describing the structural, energetic, electronic, magnetic, and vibrational properties of TMCs, challenging the traditional perception of DFT's limitations. This review explores the design principles of SCAN and r 2 SCAN, highlights their key advancements in studying TMCs, explains the mechanisms driving these improvements, and addresses the remaining challenges in this evolving field.

Zhang, Yubo [Minjiang Collaborative Center for The↗
DOE OSTI2024

Shock Hugoniot calculations using on-the-fly machine learned force fields with ab initio accuracy

We present a framework for computing the shock Hugoniot using on-the-fly machine learned force field (MLFF) molecular dynamics simulations. In particular, we employ an MLFF model based on the kernel method and Bayesian linear regression to compute the free energy, atomic forces, and pressure, in conjunction with a linear regression model between the internal and free energies to compute the internal energy, with all training data generated from Kohn–Sham density functional theory (DFT). We verify the accuracy of the formalism by comparing the Hugoniot for carbon with recent Kohn–Sham DFT results in the literature. In so doing, we demonstrate that Kohn–Sham calculations for the Hugoniot can be accelerated by up to two orders of magnitude, while retaining ab initio accuracy. We apply this framework to calculate the Hugoniots of 14 materials in the FPEOS database, comprising 9 single elements and 5 compounds, between temperatures of 10 kK and 2 MK. We find good agreement with first principles results in the literature while providing tighter error bars. In addition, we confirm that the inter-element interaction in compounds decreases with temperature.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

A Meta-Generalized Gradient Approximation for the Cavity-Dependent Exchange-Correlation Interaction in Strongly Coupled Light–Matter Systems

Strong light–matter coupling in optical cavities enables the manipulation of chemical and physical properties without altering molecular composition. Theoretical modeling of such phenomena requires exchange-correlation (XC) functionals that account for both electron–electron and electron–photon (ep) interactions within quantum electrodynamical density functional theory (QEDFT). In this work, we develop a meta-generalized gradient approximation (meta-GGA) specifically targeting the cavity-dependent XC interaction in strongly coupled light–matter systems. This novel approximation is built upon a new semilocal polarizability approximation, which draws from the jellium-with-a-gap model, and can be extended to a “global hybrid” variant that goes beyond the isotropic model from previous approximations. The polarizability model yields significantly improved dispersion coefficients and benchmark calculations with the cavity-dependent XC functional demonstrate improved agreement with QED Hartree–Fock (QED-HF) reference energies. Application to the regioselectivity of brominated nitrobenzene intermediates reveals the functional’s capacity to capture cavity-induced energetic shifts. In conclusion, our results advance the Jacob’s ladder of functionals for QEDFT and provide a practical tool for modeling polaritonic chemistry.

Approximation↗
DOE OSTI2026

First-principles simulation of a shocked H-He mixture along the principal Hugoniot

Recent laser-shock experiments on an H–He mixture containing 11% helium (atomic fraction) have suggested the presence of an immiscibility region inside Jupiter. Reflectivity measurements were used as the primary diagnostic of H–He demixing, with discontinuities in the optical reflectivity proposed as a signature of phase separation under conditions relevant to Jupiter's interior. Here, we investigate shock-compressed H–He using ab initio molecular dynamics simulations with optical properties evaluated within the Kubo–Greenwood formalism. The equation of state and ionic configurations were obtained using the thermal Tr 2 SCANL meta-GGA exchange–correlation (XC) functional, while optical properties were computed using the recently developed RS-KDT0 range-separated thermal hybrid XC, which provides state-of-the-art accuracy for band-gap predictions in the warm dense matter regime. The calculated reflectivity shows overall good agreement with experimental measurements; however, no discontinuity is observed at elevated temperatures. Moreover, the reflectivity predictions for the mixed system are consistent with the experimental measurements in the temperature range where the mixture is inferred to be demixed. Furthermore, these results suggest that reflectivity alone may not provide a unique or sensitive diagnostic of H–He demixing at low helium concentrations under these conditions.

Density functional calculations↗
NASA NTRS2007

Direct Calculation of the Scattering Amplitude Without Partial Wave Decomposition: Inclusion of Correlation Effects - III

In the first two papers in this series, we developed a method for studying electron-hydrogen scattering that does not use partial wave analysis. We constructed an ansatz for the wave function in both the static and static exchange approximations and calculated the full scattering amplitude. Here we go beyond the static exchange approximation, and include correlation in the wave function via a modified polarized orbital. This correlation function provides a significant improvement over the static exchange approximation: the resultant elastic scattering amplitudes are in very good agreement with fully converged partial wave calculations for electron-hydrogen scattering. A fully variational modification of this approach is discussed in the conclusion of the article Popular summary of Direct calculation of the scattering amplitude without partial wave expansion. III ....." by J. Shertzer and A. Temkin. In this paper we continue the development of In this paper we continue the development of a new approach to the way in which researchers have traditionally used to calculate the scattering cross section of (low-energy) electrons from atoms. The basic mathematical problem is to solve the Schroedinger Equation (SE) corresponding the above physical process. Traditionally it was always the case that the SE was reduced to a sequence of one-dimensional (ordinary) differential equations - called partial waves which were solved and from the solutions "phase shifts" were extracted, from which the scattering cross section was calculated.

Shertzer, Janine↗
DOE OSTI2025

Free-energy orbital-free density functional theory: recent developments, perspective, and outlook

By summarizing the constraint-based development of orbital-free free-energy density functional approximations, we provide a perspective on progress over the last 15 years, the limitations of existing functionals, and the challenges awaiting resolution. We outline the chronology of the development of noninteracting and exchange-correlation free-energy orbital-free functionals and summarize the theoretical basis of existing local density approximation, second-order approximation, generalized gradient approximation (GGA), and meta-GGAs. We discuss limitations and challenges such as problems with thermodynamic derivatives, free-energy nonadditivity and the closely related issue of all-electron versus valence-only local pseudo-potential performance.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1976

Metal interfaces - Adhesive energies and electronic barriers

We report a fully self-consistent calculation of the electron number density, barrier height and adhesive energy as a function of separation in an aluminum-aluminum (100) contact. The local density approximation is used for exchange and correlation. The electron number density and barrier heights are strong functions of the separation. The range of strong chemical bonding is about 0.2 nm.

Ferrante, J.↗
DOE OSTI2024

Scalable learning of potentials to predict time-dependent Hartree–Fock dynamics

We propose a framework to learn the time-dependent Hartree–Fock (TDHF) inter-electronic potential of a molecule from its electron density dynamics. Although the entire TDHF Hamiltonian, including the inter-electronic potential, can be computed from first principles, we use this problem as a testbed to develop strategies that can be applied to learn a priori unknown terms that arise in other methods/approaches to quantum dynamics, e.g., emerging problems such as learning exchange–correlation potentials for time-dependent density functional theory. We develop, train, and test three models of the TDHF inter-electronic potential, each parameterized by a four-index tensor of size up to 60 × 60 × 60 × 60. Two of the models preserve Hermitian symmetry, while one model preserves an eight-fold permutation symmetry that implies Hermitian symmetry. Across seven different molecular systems, we find that accounting for the deeper eight-fold symmetry leads to the best-performing model across three metrics: training efficiency, test set predictive power, and direct comparison of true and learned inter-electronic potentials. All three models, when trained on ensembles of field-free trajectories, generate accurate electron dynamics predictions even in a field-on regime that lies outside the training set. To enable our models to scale to large molecular systems, we derive expressions for Jacobian-vector products that enable iterative, matrix-free training.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1969

Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

Smith, J. R.↗
DOE OSTI2026

When Do Band Gap Calculations Agree with Experiments in Monolayer-Protected Cu 14 and Au 20 Atomically Precise Nanoclusters? A (TD)-DFT Comparison of HOMO–LUMO, Fundamental, Optical, and Electrochemical Energy Gaps

In view of the tremendous progress in atomically precise metal nanoclusters where electrochemical and optical energetics are routinely supported by computations to establish structure−function correlations, we explore the relationship between different protocols for measuring and computing band gaps of two distinct organic ligand-protected nanoclusters: [Cu 14 H 10 (MBN) 3 (PPh 3 ) 8 ] + and Au 20 (TBBT) 16 . Through UV/visible spectroscopy and differential pulse voltammetry, we measure optical and electrochemical band gaps in those systems. We then compare these experimentally determined gaps to HOMO−LUMO gaps, fundamental gaps, vertical excitation energies, and E o ox − E o red potentials computed using different density functional theory (DFT) or time-dependent DFT (TDDFT) methods. Specifically, in both copper and gold nanoclusters, we test the effect of truncating inert ligands from the model and compare density functionals with varying degrees of Hartree−Fock (HF) exchange from 0 to 50%, range-separated hybrids with a varying long-range tuning parameter, different correlation functionals, basis sets, and (equilibrium and nonequilibrium) continuum solvation models. Despite having different frontier orbital characters (the copper nanocluster has a metal-to-ligand charge transfer character while the gold nanocluster has metal-centered frontier orbitals), both nanoclusters display a similar sensitivity of the HOMO−LUMO gap to the HF exchange that is partially mitigated when computing the fundamental, optical, and electrochemical gaps. Other factors, such as the nature of the correlation functional, basis set, and geometry relaxation, have a considerably smaller effect on computed band gaps in these systems. Overall, this work provides guidelines for factors of varied importance for correlating computed and experimental band gap values.

Chemical calculations↗
NASA NTRS1978

The chemical activities of the Viking biology experiments and the arguments for the presence of superoxides, peroxides, gamma-Fe2O3 and carbon suboxide polymer in the Martian soil

The evolution of N2, Ar, O2, and CO2 from Martian soil as a function of humidity in the Gas Exchange Experiment are correlated with the mean level of water vapor in the Martian atmosphere. All but O2 are associated with desorption. The evolution of oxygen is consistent with the presence of alkaline earth and alkali metal superoxides; and their peroxides and the gamma-Fe2O3 in the soil can account for the generation of radioactive gas in the Labeled Release Experiment. The slower evolution of CO2 from both the Gas Exchange Experiment and the Labeled Release Experiment are associated with the direct oxidation of organics by gamma-Fe2O3. The Pyrolytic Release Experiment's second peak may be carbon suboxide as demonstrated by laboratory experiments. A necessary condition is that the polymer exists in the Martian soil. We ascribe the activity of the surface samples to the reaction of Martian particulates with an anhydrous CO2 atmosphere activated by uv and ionizing radiations. The surface particles are ultimately altered by exposure to small but significant amounts of water at the sites. From the working model, we have predicted the peculiar nature of the chemical entities and demonstrated that the model is justified by laboratory data. The final confirmation of this model will entail a return to Mars, but the nature and implications of this chemistry for the Martian surface is predicted to reveal even more about Mars with further simulations in the laboratory.

long duration↗
DOE OSTI2024

Efficient simulations of charge density waves in the transition metal Dichalcogenide TiSe 2

Charge density waves (CDWs) in transition metal dichalcogenides are the subject of growing scientific interest due to their rich interplay with exotic phases of matter and their potential technological applications. Here, using density functional theory with advanced meta-generalized gradient approximations (meta-GGAs) and linear response time-dependent density functional theory (TDDFT) with state-of-the-art exchange-correlation kernels, we investigate the electronic, vibrational, and optical properties in 1T-TiSe 2 with and without CDW. In both bulk and monolayer TiSe 2 , the electronic bands and phonon dispersions in either normal or CDW (semiconducting) phase are described well via meta-GGAs, which separate the valence and conduction bands just as HSE06 does but with significantly more computational feasibility. The experimentally observed humps of electron energy loss spectroscopy are successfully reproduced in TDDFT. Our work opens the door to simulating these complexities in CDW compounds from first principles by revealing meta-GGAs as an accurate low-cost alternative to HSE06.

Electronic properties and materials↗
NASA NTRS1987

Inclusion of electron correlation for the target wave function in low- to intermediate-energy e-N2 scattering

In a recent calculation, an exact exchange method was developed for use in the partial-differential-equation approach to electron-molecule scattering and was applied to e-N2 scattering in the fixed-nuclei approximation with an adiabatic polarization potential at low energies (0-10 eV). Integrated elastic cross sections were calculated and found to be lower than experiment at energies both below and above the Pi(g) resonance. It was speculated at that time that improved experimental agreement could be obtained if a correlated target representation were used in place of the uncorrelated one. The present paper implements this suggestion and demonstrates the improved agreement. These calculations are also extended to higher energies (0-30 eV) so asd to include the Sigma(u) resonance. Some discrepancies among the experiments and between experiment and the various calculations at very low energy are noted.

Weatherford, C. A.↗
NASA NTRS1988

Correlation of macro and micro cardiovascular function during weightlessness and simulated weightlessness

The investigation of cardiovascular function necessarily involves a consideration of the exchange of substances at the capillary. If cardiovascular function is compromised or in any way altered during exposure to zero gravity in space, then it stands to reason that microvascular function is also modified. We have shown that an increase in cardiac output similar to that reported during simulated weightlessness is associated with a doubling of the number of post-capillary venules and a reduction in the number of arterioles by 35%. If the weightlessness of space travel produces similar changes in cardiopulmonary volume and cardiac output, a reasonable expectation is that astronauts will undergo venous neovascularization. We have developed an animal model in which to correlate microvascular and systemic cardiovascular function. The microcirculatory preparation consists of a lightweight, thermo-neutral chamber implanted around intact skeletal muscle on the back of a rat. Using this technique, the performed microvasculature of the cutaneous maximus muscle may be observed in the conscious, unanesthetized animal. Microcirculatory variables which may be obtained include venular and arteriolar numbers, lengths and diameters, single vessel flow velocities, vasomotion, capillary hematocrit anastomoses and orders of branching. Systemic hemodynamic monitoring of cardiac output by electromagnetic flowmetry, and arterial and venous pressures allows correlation of macro- and microcirculatory changes at the same time, in the same animal. Observed and calculated hemodynamic variables also include pulse pressure, heart rate, stroke volume, total peripheral resistance, aortic compliance, minute work, peak aortic flow velocity and systolic time interval. In this manner, an integrated assessment of total cardiovascular function may be obtained in the same animal without the complicating influence of anesthetics.

NASA Discipline Number 00-00↗
DOE OSTI2025

Atomistic characterization of hydration-dependent fuel cell ionomer nanostructure: validation by vibrational spectroscopy

The development of Nafion alternatives for fuel cells and electrolyzers requires a fundamental understanding of hydration-dependent ion-exchange site acid/base chemistry. We present here reactive force field (ReaxFF) molecular dynamics (MD) simulations of Nafion at varying molar water/ion-exchange-site ratios (λ), which we correlate to our experimental and density functional theory-based vibrational spectra. ReaxFF describes the formation and breaking of covalent bonds, enabling simulations of proton exchange between sulfonic acid/sulfonate groups and water/hydronium. Our MD simulations determine the λ-dependent equilibrium proportions of protonated and deprotonated sites. We find that protonated sites persist across all λ from 0 to 20, challenging the widely accepted notion that all sites are ionized above a threshold λ value (e.g., 3 or 4). Our simulations generate hundreds of realistic exchange site environments, the characterization of which are based on 6 Å radii sulfur-centered ‘inner-spheres’. These inner- and outer-sphere regions elucidate an interplay of stereoelectronic factors that influence protonation states, including the number of inner-sphere waters (Λ). Our simulations produce broad λ-dependent distributions of Λ values, representing non-uniform exchange site hydration. Moreover, we demonstrate that these distributions are specific to both protonated and deprotonated sites, with significant overlap between the two distributions for all non-zero λ. These distributions underpin the IR spectra of hydrated membranes, with each exchange site contributing an IR spectrum characteristic of its protonation state and Λ. We expect that these nanostructural characterizations of Nafion exchange sites will contribute to the development of new ionomers.

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

Comparing ab initio and quantum-kinetic approaches to electron transport in warm dense matter

Accurate knowledge of the electronic transport properties of warm dense matter is one of the main concerns of research in high-energy-density physics. Three modern approaches with vastly different levels of fidelity are reviewed and compared: the Kubo–Greenwood (KG) approach based on density-functional-theory molecular dynamics simulations (QMD), quantum kinetic theory based on average-atom models, and time-dependent density functional theory. Throughout, emphasis is placed on the connection between static properties of the electrons (e.g., density of states) and transport properties. Overall, it is found that whenever the conduction electrons can be modeled as being nearly free, fair to excellent agreement is found between QMD and kinetic theory approaches. Such a circumstance is required for modeling warm dense matter as a plasma of ions and free electrons, which is assumed in most kinetic theory approaches. The sensitivity of transport properties to the electronic structure is further highlighted by comparing different exchange–correlation approximations in QMD and KG calculations. It is found that the inclusion of exact exchange via thermal hybrid functionals can make a pronounced impact on electrical and thermal conduction in warm dense matter. We also investigate dynamic screening physics via kinetic theory and time-dependent density functional theory calculations of the mean free path of an electron in a hot dense plasma. In sum, we identify three axes along which to make progress in predicting electron transport in warm dense matter.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1991

Validation of chemistry models employed in a particle simulation method

The chemistry models employed in a statistical particle simulation method, as implemented in the Intel iPSC/860 multiprocessor computer, are validated and applied. Chemical relaxation of five-species air in these reservoirs involves 34 simultaneous dissociation, recombination, and atomic-exchange reactions. The reaction rates employed in the analytic solutions are obtained from Arrhenius experimental correlations as functions of temperature for adiabatic gas reservoirs in thermal equilibrium. Favorable agreement with the analytic solutions validates the simulation when applied to relaxation of O2 toward equilibrium in reservoirs dominated by dissociation and recombination, respectively, and when applied to relaxation of air in the temperature range 5000 to 30,000 K. A flow of O2 over a circular cylinder at high Mach number is simulated to demonstrate application of the method to multidimensional reactive flows.

Haas, Brian L.↗
NASA NTRS1991

Relationships between CH4 emission, biomass, and CO2 exchange in a subtropical grassland

Methane flux was linearly correlated with plant biomass (r = 0.97, n = 6 and r = 0.95, n = 8) at two locations in a Florida Everglades Cladium marsh. One location, which had burned 4 months previously, exhibited a greater increase in methane flux as a function of biomass relative to sites at an unburned location. However, methane flux data from both sites fit a single regression (r = 0.94, n = 14) when plotted against net CO2 exchange suggesting that either methanogenesis in Everglades marl sediments is fueled by root exudation below ground, or that factors which enhance photosynthetic production and plant growth are also correlated with methane production and flux in this oligotrophic environment. The data presented are the first to show a direct relationship between spatial variability in plant biomass, net ecosystem production, and methane emission in a natural wetland.

Whiting, Gary J.↗