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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Origin of the “odd” behavior in the ultraviolet photochemistry of ozone

Significance This study solves a 30-y mystery about the origin of dramatic oscillations in the quantum product states of 16 O 3 upon photodissociation. Ozone is a key component of the atmosphere and undergoes complex cycles of formation and destruction by photodissociation and reaction. These dynamics are a rich proving ground for theories of quantum reaction dynamics as well as subtleties such as nuclear spin-statistics and symmetry. A previous theory constructed to explain the observed oscillations, although plausible, was not fully consistent with experimental measurements. Our quantum model and calculations show conclusively the origin of the effect, and match new more detailed experiments.

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

Advanced Fuel Cycle Cost Basis Report: Supporting Documents 2 Production Based Costing

The purpose of this section is to outline a method of cost analysis whereby a significantly better representation of “should achieve” costs may be attained for NOAK systems. Based on economists’ notions of producer theory, and grounded in the cost analysts’ and project managers’ tool called the Work Breakdown Structure (WBS), this section describes best practices in cost estimation. It then illustrates how the Code of Accounts (COA) structure, developed by the Economic Modeling Working Group (EMWG) of the Generation IV International Forum in “Cost Estimating Guidelines for Generation IV Nuclear Energy Systems [EMWG 2007] (hereafter “Gen IV Guidelines Document”), can be used to differentiate “should achieve” versus “did experience” costs.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Selecting the independent coordinates of manifolds with large aspect ratios

Many manifold embedding algorithms fail apparently when the data manifold has a large aspect ratio (such as a long, thin strip). Here, we formulate success and failure in terms of finding a smooth embedding, showing also that the problem is pervasive and more complex than previously recognized. Mathematically, success is possible under very broad conditions, provided that embedding is done by carefully selected eigenfunctions of the Laplace-Beltrami operator Δ. Hence, we propose a bicriterial Independent Eigencoordinate Selection (IES) algorithm that selects smooth embeddings with few eigenvectors. The algorithm is grounded in theory, has low computational overhead, and is successful on synthetic and large real data.

Meila, Marina↗
DOE OSTI2022

Correlation energy of the uniform electron gas determined by ground-state conditional probability density functional theory

Conditional-probability density functional theory (CP-DFT) is a formally exact method for finding correlation energies from Kohn-Sham DFT without evaluating an explicit energy functional. We present details on how to generate accurate exchange-correlation energies for the ground-state uniform gas. We also use the exchange hole in a CP antiparallel spin calculation to extract the high-density limit. We give a highly accurate analytic solution to the Thomas-Fermi model for this problem, showing its performance relative to Kohn-Sham and may be useful at high temperatures. We explore several approximations to the CP potential. Furthermore, results are compared to accurate parameterizations for both exchange-correlation energies and holes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Regularized machine learning on molecular graph model explains systematic error in DFT enthalpies

Abstract A major goal of materials research is the discovery of novel and efficient heterogeneous catalysts for various chemical processes. In such studies, the candidate catalyst material is modeled using tens to thousands of chemical species and elementary reactions. Density Functional Theory (DFT) is widely used to calculate the thermochemistry of these species which might be surface species or gas-phase molecules. The use of an approximate exchange correlation functional in the DFT framework introduces an important source of error in such models. This is especially true in the calculation of gas phase molecules whose thermochemistry is calculated using the same planewave basis set as the rest of the surface mechanism. Unfortunately, the nature and magnitude of these errors is unknown for most practical molecules. Here, we investigate the error in the enthalpy of formation for 1676 gaseous species using two different DFT levels of theory and the ‘ground truth values’ obtained from the NIST database. We featurize molecules using graph theory. We use a regularized algorithm to discover a sparse model of the error and identify important molecular fragments that drive this error. The model is robust to rigorous statistical tests and is used to correct DFT thermochemistry, achieving more than an order of magnitude improvement.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Relativistic spin dynamics for vector mesons

We propose a relativistic theory for spin density matrices of vector mesons based on Kadanoff-Baym equations in the closed-time-path formalism. The theory puts the calculation of spin observables such as the spin density matrix element ρ 00 for vector mesons on a solid ground. Within the theory we formulate ρ 00 for ϕ mesons into a factorization form in separation of momentum and spacetime variables. We argue that the main contribution to ρ 00 at lower energies should be from the ϕ fields that can polarize the strange quark and antiquark in the same way as electromagnetic fields. The key observation is that there is correlation inside the ϕ meson wave function between the ϕ field that polarizes the strange quark and that polarizes the strange antiquark. This is reflected by the fact that the contributions to ρ 00 are all in squares of fields that are nonvanishing even if the fields may strongly fluctuate in spacetime. The fluctuation of strong force fields can be extracted from ρ 00 of unflavored vector mesons as links to fundamental properties of quantum chromodynamics. Published by the American Physical Society 2024

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Using isotope shift for testing nuclear theory: The case of nobelium isotopes

We calculate field isotope shifts for nobelium atoms using nuclear charge distributions which come from different nuclear models.We demonstrate that comparing calculated isotope shifts with experiment can serve as a testing ground for nuclear theories. It also provides a way of extracting parameters of nuclear charge distribution beyond nuclear root mean square (rms) radius, e.g., parameter of quadrupole deformation β. The measurements of at least two atomic transitions is needed to disentangle the contributions of the changes in deformation and nuclear rms radius into field isotopic shift. We argue that a previous interpretation of the isotope measurements in terms of δ < r 2 > between 252,254 No isotopes should be amended when nuclear deformation is taken into account. As a result, we calculate isotope shifts for other known isotopes and for hypothetically metastable isotope 286 No for which the predictions of nuclear models differ substantially.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Reexamining the variational two-particle reduced density matrix for nuclear systems

We report that in most nuclear many-body methods, observables are calculated using many-body wave functions explicitly. The variational two-particle reduced density matrix method is one of the few exceptions to the rule. Ground-state energies of both closed-shell and open-shell nuclear systems can indeed be evaluated by minimizing a constrained linear functional of the two-particle reduced density matrix. However, it has virtually never been used in nuclear theory, because nuclear ground states were found to be well overbound, contrary to those of atoms and molecules. Consequently, we introduced new constraints in the nuclear variational two-particle reduced density matrix method, developed recently for atomic and molecular systems. Our calculations then show that this approach can provide a proper description of nuclear systems where only valence neutrons are included. For the nuclear systems where both neutrons and protons are active, however, the energies obtained with the variational two-particle reduced density matrix method are still overbound. The possible reasons for the noticed discrepancies and solutions to this problem will be discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Ground state wave functions for single-band Hubbard models from the Gutzwiller conjugate gradient minimisation theory

The Gutzwiller conjugate gradient minimisation (GCGM) theory is an ab initio quantum many-body theory for computing the ground-state properties of infinite systems. Previous applications of GCGM provides satisfying accuracy of ground-state energy of Hubbard models. In the current work, we address the problem of whether the obtained wave function is a good approximation for the true ground state by comparing the correlation functions with the benchmark data. Additionally, our results confirms the accuracy of the reproduced ground state of the regular Hubbard model, but with some exception for the frustrated Hubbard model.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Systematically localizable operators for quantum simulations of quantum field theories

Correlations and measures of entanglement in ground-state wave functions of relativistic quantum field theories are spatially localized over length scales set by the mass of the field. We utilize this localization to design digital quantum circuits for preparing the ground states of lattice scalar quantum field theories. Controlled rotations that are exponentially localized in their position-space extent are found to provide exponentially convergent wave function fidelity. These angles scale with the correlation between sites and the classical two-point correlation function, as opposed to the more localized mutual information or the hyperlocalized (1×1)-site negativity. We anticipate that further investigations will uncover quantum circuit designs with controlled rotations dictated by the measures of entanglement. This work is expected to impact quantum simulations of systems of importance to nuclear physics, high-energy physics, and basic energy sciences research.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Ground-state properties of the Hubbard model in one and two dimensions from the Gutzwiller conjugate gradient minimization theory

We introduce Gutzwiller conjugate gradient minimization (GCGM) theory, an ab initio quantum many-body theory for computing the ground-state properties of infinite systems. GCGM uses the Gutzwiller wave function but does not use the commonly adopted Gutzwiller approximation (GA), which is a major source of inaccuracy. Instead, the theory uses an approximation that is based on the occupation probability of the on-site configurations, rather than approximations that decouple the site-site correlations as used in the GA. We test the theory in the one-dimensional and two-dimensional Hubbard models at various electron densities and find that GCGM reproduces energies and double occupancies in reasonable agreement with benchmark data at a very small computational cost.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Dissipative ground state preparation in ab initio electronic structure theory

Dissipative engineering is a powerful tool for quantum state preparation, and has drawn significant attention in quantum algorithms and quantum many-body physics in recent years. In this work, we introduce a novel approach using the Lindblad dynamics to efficiently prepare the ground state for general ab initio electronic structure problems on quantum computers, without variational parameters. These problems often involve Hamiltonians that lack geometric locality or sparsity structures, which we address by proposing two generic types of jump operators for the Lindblad dynamics. Type-I jump operators break the particle number symmetry and should be simulated in the Fock space. Type-II jump operators preserves the particle number symmetry and can be simulated more efficiently in the full configuration interaction space. For both types of jump operators, we prove that in a simplified Hartree-Fock framework, the spectral gap of our Lindbladian is lower bounded by a universal constant. For physical observables such as energy and reduced density matrices, the convergence rate of our Lindblad dynamics with Type-I jump operators remains universal, while the convergence rate with Type-II jump operators only depends on coarse grained information such as the number of orbitals and the number of electrons. To validate our approach, we employ a Monte Carlo trajectory-based algorithm for simulating the Lindblad dynamics for full ab initio Hamiltonians, demonstrating its effectiveness on molecular systems amenable to exact wavefunction treatment.

Quantum chemistry↗
DOE OSTI2022

Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations

Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf–O or Hf–B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cluster quantum chemical calculations on these systems. We compute full potential energy curves, excitation energies, ionization energies, electronic configurations, and spectroscopic parameters with large quadruple-ζ and quintuple-ζ quality correlation consistent basis sets. We also investigate equilibrium chemical bonding patterns and effects of correlating core electrons on property predictions. Differences in the ground state electron configuration of HfB(X 4 Σ - ) and HfO(X 1 Σ + ) lead to a significantly stronger bond in HfO than HfB, as judged by both dissociation energies and equilibrium bond distances. We extend our analysis to the chemical bonding patterns of the isovalent HfX (X = O, S, Se, Te, and Po) series and observe similar trends. We also note a linear trend between the decreasing value of the dissociation energy (D e ) from HfO to HfPo and the singlet–triplet energy gap (ΔE S–T ) of the molecule. Finally, we compare these benchmark results to those obtained using density functional theory (DFT) with 23 exchange–correlation functionals spanning multiple rungs of “Jacob’s ladder.” When comparing DFT errors to coupled cluster reference values on dissociation energies, excitation energies, and ionization energies of HfB and HfO, we observe semi-local generalized gradient approximations to significantly outperform more complex and high-cost functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Repartitioning the Hamiltonian in many-body second-order Brillouin–Wigner perturbation theory: Uncovering new size-consistent models

Second-order Møller-Plesset perturbation theory is well-known as a computationally inexpensive approach to the electron correlation problem that is size-consistent with a size-consistent reference but fails to be regular. On the other hand, the less well-known many-body version of Brillouin-Wigner perturbation theory has the reverse properties: it is regular but fails to be size-consistent when used with the standard MP partitioning. Consequently, its widespread use remains limited. In this work, we analyze the ways in which it is possible to use alternative non-MP partitions of the Hamiltonian to yield variants of BW2 that are size-consistent as well as regular. We show that there is a vast space of such BW2 theories and also show that it is possible to define a repartitioned BW2 theory from the ground state density alone, which regenerates the exact correlation energy. We also provide a general recipe for deriving regular, size-consistent, and size-extensive partitions from physically meaningful components, and we apply the result to small model systems. The scope of these results appears to further set the stage for a revival of BW2 in quantum chemistry.

Ab initio perturbation↗
DOE OSTI2021

Nonadiabatic couplings from a variational excited state method based on constrained DFT

Excited Costrained Density Functional Theory (XCDFT) is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. Here, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H 3 , the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT’s energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Theoretical predictive screening of noble-metal-containing M 3 AuC 2 (M = Ti, V, and Cr) MAX phases

Using first-principles density functional theory (DFT), the ground state physical properties of the newly synthesized noble-metal-containing Ti 3 AuC 2 MAX phase have been investigated. The effect of transition-element Ti replacement (V and Cr) on physical properties, including structural, elastic, electronic, thermal, and optical are presented. The optimized lattice parameters of Ti 3 AuC 2 MAX phase are in good agreement with the experimental values and decrease when we replace Ti with V and then Cr. The magnetic properties of M 3 AuC 2 are predicted by using generalized gradient approximation (GGA) incorporating onsite electron correlation parameter (Hubbard U parameter) within DFT. Out of three studied MAX phases, V 3 AuC 2 and Cr 3 AuC 2 phases exhibit magnetism. The thermodynamical stability of M 3 AuC 2 (M = Ti, V, and Cr) phases is discussed by the formation enthalpy with respect to their most competing phases. The electronic structure reveals that these phases have metallic nature and are electrically anisotropic. The M-element replacement has an effect on the bonding properties of M 3 AuC 2 . The bonding between M-C is in the order of Cr 3 AuC 2 > V 3 AuC 2 > Ti 3 AuC 2 according to their peak positions and heights of density of states in the occupied site, which is also confirmed from the charge density distribution. The elastic properties indicate that M 3 AuC 2 phases are ductile, machinable, less stiff, and better resistant to thermal shock and are elastically anisotropic. To understand the properties of M 3 AuC 2 for the extreme environment, we employed a quasi-harmonic Debye model at the pressure and temperature range of 0–50 GPa and 0–1600 K, respectively. Additionally, we evaluated thermal conductivity and melting temperature to further understand the potential of these MAX phases in coating applications at elevated temperature. In relation to optical properties, these MAX phases have a reasonable absorption coefficient in the visible as well as in the ultra-violet regions. The reflectivity of M 3 AuC 2 phases is polarization dependent and of 45 % against the visible region, which reveals its potential as coating material to minimize solar heating.

312 MAX phases↗
DOE OSTI2024

Precise Modulation of CO 2 Sorption in Ti 8 Ce 2 –Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti 8 Ce 2 -oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti 8 Ce 2 -BA (BA denotes benzoic acid) manifests a distinctive two-step profile during CO 2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in-situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between CO 2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. Furthermore, these insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

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

Electrostatic upper-hybrid mode instability driven by a ring electron distribution

Quasi electrostatic fluctuations in the upper-hybrid frequency range are commonly detected in the planetary magnetospheric environment. The origin of such phenomena may relate to the instability driven by a loss-cone feature associated with the electrons populating the dipole-like magnetic field. The present paper carries out a one-dimensional electrostatic particle-in-cell simulation accompanied by a reduced quasilinear kinetic theoretical analysis to investigate the dynamics of the upper-hybrid mode instability driven by an initial ring electron distribution function, which is a form of loss-cone distribution. A favorable comparison is found between the two approaches, which shows that the reduced quasilinear theory, which is grounded in the concept of a model of the particle distribution function that is assumed to maintain a fixed mathematical form except that the macroscopic parameters that define the distribution are allowed to evolve in time, can be an effective tool in the study of plasma instabilities, especially if it is guided by and validated against the more rigorous simulation result.

Physics↗