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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 OSTI2021

Importance of charge self-consistency in first-principles description of strongly correlated systems

First-principles approaches have been successful in solving many-body Hamiltonians for real materials to an extent when correlations are weak or moderate. As the electronic correlations become stronger often embedding methods based on first-principles approaches are used to better treat the correlations by solving a suitably chosen many-body Hamiltonian with a higher level theory. The success of such embedding theories, often referred to as second-principles, is commonly measured by the quality of self-energy Σ which is either a function of energy or momentum or both. However, Σ should, in principle, also modify the electronic eigenfunctions and thus change the real space charge distribution. While such practices are not prevalent, some works that use embedding techniques do take into account these effects. In such cases, choice of partitioning, of the parameters defining the correlated Hamiltonian, of double-counting corrections, and the adequacy of low-level Hamiltonian hosting the correlated subspace hinder a systematic and unambiguous understanding of such effects. Further, for a large variety of correlated systems, strong correlations are largely confined to the charge sector. Then an adequate nonlocal low-order theory is important, and the high-order local correlations embedding contributes become redundant. Here we study the impact of charge self-consistency within two example cases, TiSe 2 and CrBr 3 , and show how real space charge re-distribution due to correlation effects taken into account within a first-principles Green’s function-based many-body perturbative approach is key in driving qualitative changes to the final electronic structure of these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multiscale Models for Fibril Formation: Rare Events Methods, Microkinetic Models, and Population Balances

Amyloid fibrils are thought to grow by a two-step dock-lock mechanism. However, previous simulations of fibril formation (i) overlook the bi-molecular nature of the docking step and obtain rates with first-order units, or (ii) superimpose the docked and locked states when computing the potential of mean force for association and thereby muddle the docking and locking steps. Here, we developed a simple microkinetic model with separate locking and docking steps and with the appropriate concentration dependences for each step. We constructed a simple model comprised of chiral dumbbells that retains qualitative aspects of fibril formation. We used rare events methods to predict separate docking and locking rate constants for the model. The rate constants were embedded in the microkinetic model, with the microkinetic model embedded in a population balance model for “bottom-up” multiscale fibril growth rate predictions. These were compared to “top-down” results using simulation data with the same model and multiscale framework to obtain maximum likelihood estimates of the separate lock and dock rate constants. We used the same procedures to extract separate docking and locking rate constants from experimental fibril growth data. Our multiscale strategy, embedding rate theories, and kinetic models in conservation laws should help to extract docking and locking rate constants from experimental data or long molecular simulations with correct units and without compromising the molecular description.

Shayesteh Zadeh, Armin (ORCID:0000000299896710)↗
NASA NTRS1985

Constitutive Modeling of Superalloy Single Crystals and Directionally Solidified Materials

A unified viscoplastic constitutive relation based on crystallographic slip theory was developed for the deformation analysis of nickel base face centered cubic superalloy single crystals at elevated temperature. The single crystal theory is embedded in a self consistent method to derive a constitutive relation for a directionally solidified material comprised of a polycrystalline aggregate of columnar cylindrical grains. One of the crystallographic axes of the cylindrical crystals points in the columnar direction while the remaining crystallographic axes are oriented at random in the basal plane perpendicular to the columnar direction. These constitutive formulations are coded in FORTRAN for use in nonlinear finite element and boundary element programs.

Walker, K. P.↗
NASA NTRS1989

Development of a funding, cost, and spending model for satellite projects

The need for a predictive budget/funging model is obvious. The current models used by the Resource Analysis Office (RAO) are used to predict the total costs of satellite projects. An effort to extend the modeling capabilities from total budget analysis to total budget and budget outlays over time analysis was conducted. A statistical based and data driven methodology was used to derive and develop the model. Th budget data for the last 18 GSFC-sponsored satellite projects were analyzed and used to build a funding model which would describe the historical spending patterns. This raw data consisted of dollars spent in that specific year and their 1989 dollar equivalent. This data was converted to the standard format used by the RAO group and placed in a database. A simple statistical analysis was performed to calculate the gross statistics associated with project length and project cost ant the conditional statistics on project length and project cost. The modeling approach used is derived form the theory of embedded statistics which states that properly analyzed data will produce the underlying generating function. The process of funding large scale projects over extended periods of time is described by Life Cycle Cost Models (LCCM). The data was analyzed to find a model in the generic form of a LCCM. The model developed is based on a Weibull function whose parameters are found by both nonlinear optimization and nonlinear regression. In order to use this model it is necessary to transform the problem from a dollar/time space to a percentage of total budget/time space. This transformation is equivalent to moving to a probability space. By using the basic rules of probability, the validity of both the optimization and the regression steps are insured. This statistically significant model is then integrated and inverted. The resulting output represents a project schedule which relates the amount of money spent to the percentage of project completion.

Johnson, Jesse P.↗
NASA NTRS1996

Simulation of Fatigue Behavior of High Temperature Metal Matrix Composites

A generalized relatively new approach is described for the computational simulation of fatigue behavior of high temperature metal matrix composites (HT-MMCs). This theory is embedded in a specialty-purpose computer code. The effectiveness of the computer code to predict the fatigue behavior of HT-MMCs is demonstrated by applying it to a silicon-fiber/titanium-matrix HT-MMC. Comparative results are shown for mechanical fatigue, thermal fatigue, thermomechanical (in-phase and out-of-phase) fatigue, as well as the effects of oxidizing environments on fatigue life. These results show that the new approach reproduces available experimental data remarkably well.

Tong, Mike T.↗
DOE OSTI2023

Multi-site reaction dynamics through multi-fragment density matrix embedding

The practical description of disordered chemical reactions, where the reactions involve multiple species at multiple sites, is presently a challenge using correlated electronic structure methods due to their high computational cost and steep scaling. Here, we describe the gradient theory of multi-fragment density matrix embedding theory, which potentially provides a minimal computational framework to model such processes at the correlated electron level. We present the derivation and implementation of the gradient theory, its validation on model systems and chemical reactions using density matrix embedding, and its application to a molecular dynamics simulation of proton transport in a small water cluster, a simple example of multi-site reaction dynamics.

Chemistry↗
DOE OSTI2020

Benchmarking an Embedded Adaptive Sampling Configuration Interaction Method for Surface Reactions: H 2 Desorption from and CH 4 Dissociation on Cu(111)

Embedded (emb-) correlated wavefunction (CW) theory enables accurate assessments of both ground- and excited-state reaction mechanisms involved in heterogeneous catalysis. Embedded multireference second-order perturbation theory (emb-MRPT2) based on reference wavefunctions generated via embedded complete active space self-consistent field (emb-CASSCF) theory is currently state-of-the-art. However, the factorial scaling of CASSCF limits the size of active space and the complexity of systems that can be studied. In this work, we assess the efficacy of an alternative CW method, adaptive sampling configuration interaction (ASCI)–which enables large active spaces to be used–for studying surface reactions. We couple ASCI with density functional embedding theory (DFET) and benchmark its performance for two reactions: H 2 desorption from and CH 4 dissociation on the Cu(111) surface. Unlike embedded complete active space second-order perturbation theory (emb-CASPT2) that accurately reproduces a measured H 2 desorption barrier, embedded ASCI, using a very large active space (though one that still comprises a small portion of the full set of orbitals) fails to do so. Adding an extra correlation term from embedded Møller–Plesset second-order perturbation theory (emb-MP2) improves the desorption barrier and endothermicity predictions. Thus, the inaccuracy of embedded ASCI comes from the missing dynamic correlation from the many other electrons and orbitals not included in the active space. For CH 4 dissociation, again embedded ASCI overestimates the dissociation barrier compared to emb-CASPT2 predictions. Adding dynamic correlation from emb-MP2 helps correct the barrier. However, this composite approach suffers from double counting of correlation within embedded ASCI followed by emb-MP2 calculations. We therefore conclude that the state-of-the-art emb-MRPT2 based on reference wavefunctions generated via emb-CASSCF remains the method of choice for studying surface reactions. emb-ASCI is useful when large active spaces beyond the limit of emb-CASSCF are essential, such as to study complex surface reactions with significant multiconfigurational character (static correlation) but weak dynamic correlation.

08 HYDROGEN↗
NASA NTRS1982

The 3-D inelastic analysis methods for hot section components: Brief description

Advanced 3-D inelastic structural/stress analysis methods and solution strategies for more accurate yet more cost-effective analysis of components subjected to severe thermal gradients and loads in the presence of mechanical loads, with steep stress and strain gradients are being developed. Anisotropy, time and temperature dependent plasticity and creep effects are also addressed. The approach is to develop four different theories, one linear and three higher order theories (polynomial function, special function, general function). The theories are progressively more complex from linear to general function in order to provide streamlined analysis capability with increasing accuracy for each hot section component and for different parts of the same component according to the severity of the local stress, strain and temperature gradients associated with hot spots, cooling holes and surface coating cracks. To further enhance the computational effectiveness, the higher order theories will have embedded singularities (cooling passages, for example) in the generic modeling region. Each of the four theories consists of three formulation models derivable from independent theoretical formulations. These formulation models are based on: (1) mechanics of materials; (2) special finite elements; and (3) an advanced formulation to be recommended by the contractor.

Chamis, C. C.↗
DOE OSTI2020

The UV fate of anomalous U(1)s and the Swampland

Massive U(1) gauge theories featuring parametrically light vectors are suspected to belong in the Swampland of consistent EFTs that cannot be embedded into a theory of quantum gravity. We study four-dimensional, chiral U(1) gauge theories that appear anomalous over a range of energies up to the scale of anomaly-cancelling massive chiral fermions. We show that such theories must be UV-completed at a finite cutoff below which a radial mode must appear, and cannot be decoupled — a Stückelberg limit does not exist. When the infrared fermion spectrum contains a mixed U(1)-gravitational anomaly, this class of theories provides a toy model of a boundary into the Swampland, for sufficiently small values of the vector mass. In this context, we show that the limit of a parametrically light vector comes at the cost of a quantum gravity scale that lies parametrically below MP1, and our result provides field theoretic evidence for the existence of a Swampland of EFTs that is disconnected from the subset of theories compatible with a gravitational UV-completion. Moreover, when the low energy theory also contains a U(1) 3 anomaly, the Weak Gravity Conjecture scale makes an appearance in the form of a quantum gravity cutoff for values of the gauge coupling above a certain critical size.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

DFT-based QM/MM with Particle-Mesh Ewald for Direct, Long-Range Electrostatic Embedding

In this work, we present a DFT-based, QM/MM implementation with long-range electrostatic embedding achieved by direct real-space integration of the particle mesh Ewald (PME) computed electrostatic potential. The key transformation is the interpolation of the electrostatic potential from the PME grid to the DFT quadrature grid, from which integrals are easily evaluated utilizing standard DFT machinery. We provide benchmarks of the numerical accuracy with choice of grid size and real-space corrections, and demonstrate that good convergence is achieved while introducing nominal computational overhead. Furthermore, the approach requires only small modification to existing software packages, as is demonstrated with our implementation in the OpenMM and Psi 4 software. After presenting convergence benchmarks, we evaluate the importance of long-range electrostatic embedding in three solute/solvent systems modeled with QM/MM. Water and BMIM/BF 4 ionic liquid were considered as "simple" and "complex" solvents respectively, with water and p-phenylenediamine (PPD) solute molecules treated at QM level of theory. While electrostatic embedding with standard real-space truncation may introduce negligible error for simple systems such as water solute in water solvent, errors become more significant when QM/MM is applied to complex solvents such as ionic liquids. An extreme example is the electrostatic embedding energy for oxidized PPD in BMIM/BF 4 for which real-space truncation produces severe error even at 2-3 nm cutoff distances. This latter example illustrates that utilization of QM/MM to compute redox potentials within concentrated electrolytes/ionic media requires carefully chosen long-range electrostatic embedding algorithms, with our presented algorithm providing a general and robust approach.

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

Singular limits in STU supergravity

Abstract We analyse the STU sectors of the four-dimensional maximal gauged supergravities with gauge groups SO(8), SO(6) ⋉ ℝ 12 and [SO(6) × SO(2)] ⋉ ℝ 12 , and construct new domain-wall black-hole solutions inD= 4. The consistent Kaluza-Klein embedding of these theories is obtained using the techniques of Exceptional Field Theory combined with the 4dtensor hierarchies, and their respective uplifts intoD= 11 and type IIB supergravities are connected through singular limits that relate the different gaugings.

Physics↗
DOE OSTI2024

Elucidating and contrasting the mechanisms for Mg and Ca sulfate ion-pair formation with multi-level embedded quantum mechanics/molecular dynamics simulations

Here, solutions and minerals containing sulfate (SO 4 2- ), and Ca 2+ and Mg 2+ cations, are ubiquitous throughout the lithosphere and are significant components of seawater, thus presenting a prototypical system for the study of strong electrolytes and crystal nucleation mechanisms. However, despite their relative abundance, key questions remain unanswered about the most fundamental atomic-level steps of their mineralization pathways and aqueous dynamics. Here, we carry out enhanced sampling multi-level molecular dynamics (MD) embedded correlated wavefunction theory simulations to elucidate ion-pairing mechanisms for Mg–SO 4 and Ca–SO 4 in concentrated aqueous solution, accurately capturing effects arising from both structural dynamics and electron exchange–correlation. We predict contact-ion-pair formation to be barrierless and highly exoergic for Ca–SO 4 , in agreement with its minimal solubility, whereas for Mg–SO 4 , solvent-shared and contact ion pairs have similar free energies, qualitatively consistent with its higher solubility. Finally, we demonstrate that brief high-temperature pre-equilibration may be utilized to accelerate convergence of free energies in blue-moon-ensemble enhanced-sampling MD.

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

Universal construction of black hole microstates

We refine and extend a recent construction of sets of black hole microstates with semiclassical interiors that span a Hilbert space of dimension e S , where S is the black hole entropy. We elaborate on the definition and properties of microstates in statistical and black hole mechanics. The gravitational description of microstates employs matter shells in the interior of the black hole, and we argue that in the limit where the shells are very heavy, the construction acquires universal validity. To this end, we show it for very wide classes of black holes; we first extend the construction to rotating and charged black holes, including extremal and near-extremal solutions, with or without supersymmetry, and we sketch how the construction of microstates can be embedded in string theory. We then describe how the approach can include general quantum corrections, near or far from extremality. For supersymmetric black holes, the microstates we construct differ from other recent constructions in that the interior excitations are not confined within the near-extremal throat. Published by the American Physical Society 2024

Astronomy & Astrophysics↗
NASA NTRS1998

Profile Evolution Simulation in Etching Systems Using Level Set Methods

Semiconductor device profiles are determined by the characteristics of both etching and deposition processes. In particular, a highly anisotropic etch is required to achieve vertical sidewalls. However, etching is comprised of both anisotropic and isotropic components, due to ion and neutral fluxes, respectively. In Ar/Cl2 plasmas, for example, neutral chlorine reacts with the Si surfaces to form silicon chlorides. These compounds are then removed by the impinging ion fluxes. Hence the directionality of the ions (and thus the ion angular distribution function, or IAD), as well as the relative fluxes of neutrals and ions determines the amount of undercutting. One method of modeling device profile evolution is to simulate the moving solid-gas interface between the semiconductor and the plasma as a string of nodes. The velocity of each node is calculated and then the nodes are advanced accordingly. Although this technique appears to be relatively straightforward, extensive looping schemes are required at the profile corners. An alternate method is to use level set theory, which involves embedding the location of the interface in a field variable. The normal speed is calculated at each mesh point, and the field variable is updated. The profile comers are more accurately modeled as the need for looping algorithms is eliminated. The model we have developed is a 2-D Level Set Profile Evolution Simulation (LSPES). The LSPES calculates etch rates of a substrate in low pressure plasmas due to the incident ion and neutral fluxes. For a Si substrate in an Ar/C12 gas mixture, for example, the predictions of the LSPES are identical to those from a string evolution model for high neutral fluxes and two different ion angular distributions.(2) In the figure shown, the relative neutral to ion flux in the bulk plasma is 100 to 1. For a moderately isotropic ion angular distribution function as shown in the cases in the left hand column, both the LSPES (top row) and rude's string method (bottom row) predict tapered profiles. The LSPES uses an AD with a FWHM = 13.5 degrees, and rude's model uses a ratio of sheath voltage to ion temperature of 50. The more anisotropic IADs produce profiles with more vertical sidewalls and a wider bottom surface, as shown in the right hand column. Here, the LSPES has an AD with a FWHM = 2 degrees, and rude's model uses a ratio of 500 of sheath voltage to ion temperature. The agreement between the LSPES and rude's model is excellent in both cases. We will present etching profiles generated by the LSPES, including calculations of the re-emitted fluxes of both neutrals and ions off of the profile walls. In addition, we will show the effect of geometric structures (overhangs, etc.) on the etching profiles. Other physical aspects, such as surface diffusion, will also be included in the model.

Hwang, Helen H.↗
DOE OSTI2020

Embedding Methods for Quantum Chemistry: Applications from Materials to Life Sciences

Quantum mechanical embedding methods hold the promise to transform not just the way calculations are performed, but to significantly reduce computational costs and improve scaling for macro molecular systems containing hundreds if not thousands of atoms. The field of embedding has grown increasingly broad with many approaches of different intersecting flavors. Here, we lay out the methods into two streams: QM:MM and QM:QM, showcasing the advantages and disadvantages of both. We provide a review of the literature, the underpinning theories including our contributions, and we highlight current applications with select examples spanning both materials and life sciences. Lastly, we conclude with prospects and future outlook on embedding, and our view on the use of universal test case scenarios for cross comparisons of the many available (and future) embedding theories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Insights into Nonelectroactive C–C Bond Formation on Cu(100) during Electrochemical CO 2 Reduction from Multiconfigurational Wavefunction Theory

Carbon–carbon (C–C) bond formation is necessary for hydrocarbon (and oxygenate) synthesis beyond methane (and formate/formic acid) during electrochemical CO and CO 2 reduction (ECOR and ECO 2 R). Cu has notable ability to form hydrocarbons compared to other pure metals. In particular, the (100) facet of face-centered cubic Cu forms ethylene competitively with H 2 and methane during both ECOR and ECO 2 R. Past simulations based on density functional theory (DFT) with standard exchange-correlation functional approximations predict fast nonelectroactive C–C bond formation channels involving adsorbed (*) CO together with another *CO, formyl (*CHO), or hydroxymethylidyne (*COH), forming OC*–*CO, OC*–CHO*, and OC*–*COH, respectively. Such simulations support the prevailing hypothesis that emergence of C 2 products is kinetically determined at the early stages of the reduction chemistry. Here we show, via simulations with more accurate many-body, i.e., “correlated”, wavefunction theory (enabled by an embedding scheme), that the coupling of *CO with a *CO or a *COH (previously predicted at the same level of theory to kinetically dominate over *CHO as the one-electron reduction product of *CO) is highly activated (kinetically impeded), with free energy barriers >1 eV, in contradiction to previous DFT-based simulations. Intriguingly, we find that the coupling of two adjacent *COHs incurs only a small barrier (<0.3 eV) and is exoergic (< –1 eV); however, given the predicted low surface mobility of *COH, the emergence of HOC*–*COH is also improbable, at least at low *COH coverages. We therefore conclude that it is highly unlikely for *CO to participate in nonelectroactive C–C bond formation on pristine Cu(100), contrary to conventional wisdom, and that the energetically favorable *COH dimerization may occur only after substantial buildup of *COH on the surface.

adsorption↗