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At least 973 records · Page 54
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DOE OSTI2026

High-Resolution Laser Spectroscopy on the Hyperfine Structure of 255Fm (𝑍=100)

We report on high-resolution laser spectroscopy of 255Fm (𝑇1/2=20 h), one of the heaviest nuclides available from reactor breeding. The hyperfine structures in two different atomic ground-state transitions at 398.4 nm and 398.2 nm were probed by in-source laser spectroscopy at the RISIKO mass separator in Mainz, using the perpendicularly illuminated laser ion source and trap (PI-LIST) high-resolution ion source. Experimental results were combined with hyperfine fields from various atomic ab initio calculations, in particular using multiconfiguration Dirac-Hartree-Fock theory, as implemented in grasp18. In this manner, the nuclear magnetic dipole and electric quadrupole moments were derived to be 𝜇=−0.75⁢(5) 𝜇N and 𝑄s=+5.84⁢(13) eb, respectively. The magnetic moment indicates occupation of the 𝜈⁢7/2⁢[613] Nilsson orbital, while the large quadrupole moment confirms strong, stable prolate deformation consistent with systematics in the heavy actinides. Comparisons with available expectation values from nuclear theory show good agreement, providing a stringent benchmark for the used theoretical models. These results revise earlier data and establish 255Fm as a reference isotope for future high-resolution studies.

Ezold, Julie [ORNL] (ORCID:0000000250550022)↗
DOE OSTI2019

A First-Principles Study of the Vacancy-Mediated Silver Impurity Diffusion in fcc Nickel

In this report, ab initio techniques (Density Functional Theory, DFT) are used to calculate the vacancy-mediated self-diffusion coefficient and impurity diffusion coefficient of silver (Ag) in pure fcc nickel (Ni). Prediction of diffusion coefficients is one of the most stringent tests of the ability of DFT calculations, because of the complex interplay of lattice constant, vacancy formation enthalpy, solute-vacancy binding enthalpy, and vibrational frequencies. The Ag diffusion and Ni self-diffusion coefficients calculated in the present work compare very favorably to previous experimental self-diffusion and Ag diffusion data. Extension of the methodology to nickel alloys is envisioned in future work.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Low-lying states and total internal partition sums of CH

The electronic structure and spin-orbit states of the CH radical have been systematically investigated using multi-reference configuration interaction (MRCI) and single-reference coupled-cluster (CC) methods. These calculations were performed in conjunction with large correlation-consistent basis sets of quadruple-, quintuple-, and sextuple-ζ quality. To achieve high accuracy, electronic energies for all states were extrapolated to the complete basis set (CBS) limit, enabling the detailed construction of potential energy curves and determination of reliable spectroscopic constants. Spin-orbit coupling effects were explicitly incorporated, and vibrational energy levels were computed via Numerov analysis. Furthermore, the resulting values exhibit good to excellent agreement with available experimental data. Dipole moment and transition dipole moment curves were evaluated to assess the opacity characteristics of CH, revealing that transitions such as Χ 2 Π (u′′ = 0) → Α 2 Δ (u′ = 0), Χ 2 Π (u′′ = 0) → Β 2 Σ − (u′ = 0), Χ 2 Π (u′′ = 0) → C 2 Σ + (u′ = 0), and Χ 2 Π (u′′ = 0) → D 2 Σ + (u′ = 3) are particularly probable. Finally, the total internal partition function sum (TIPS) of CH was computed over a broad temperature range (10–30,000 K) based on our high-accuracy ab initio results.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene

Vibronic coupling is believed to play an important role in siglet fission, wherein a photoexcited singlet exciton is converted into two triplet excitons. In the present study, we examine the role of vibronic coupling in singlet fission using polarized transient absorption microscopy and ab initio simulations on single-crystalline pentacene. It was found that singlet fission in pentacene is greatly facilitated by the vibrational coherence of a 35.0 cm(-1) phonon, where anisotropic coherence persists extensively for a few picoseconds. This coherence-preserving phonon that drives the anisotropic singlet fission is made possible by a unique cross-axial charge-transfer intermediate state. In the same fashion, this phonon was also found to predominantly drive the quantum decohence of a correlated triplet pair to form a decoupled triplet dimer. Moreover, our transient kinetic experimental data illustrates notable directional anisotropicity of the singlet fission rate in single-crystalline pentacene.

Deng, Gang-Hua↗
DOE OSTI2015

Glass-forming ability of TeO{sub 2} and temperature induced changes on the structure of the glassy, supercooled, and molten states

Polarized (VV) and depolarized (VH) Raman spectra are obtained for glassy, supercooled, and molten TeO{sub 2} at temperatures up to 1000 K in order to elucidate the temperature evolution of the pertinent structural and vibrational properties. The intrinsic tendency of the system for crystallization is avoided by means of a newly applied protocol, thereby enabling the recording of Raman spectra of pure TeO{sub 2} on going from the molten to the supercooled liquid and to the room temperature glass states. Following an appropriate fitting procedure, the revealed bands are assigned to specific modes of structural polymorphs. A weak polarised band at ∼880 cm{sup −1} is assigned to Te=O terminal stretching in agreement with the literature ab initio molecular orbital calculations. Subtle changes to the relative band intensities within the 550-900 cm{sup −1} stretching region are caused by temperature increase. The network-like structure of the glass/melt is composed by TeO{sub 4} trigonal bipyramid and TeO{sub 3} trigonal pyramid units. With increasing temperature, TeO{sub 4} units convert to TeO{sub 3} units with a concurrent increase in the number of Te=O sites resulting from cleavages within the network structure. The fraction of such terminal oxygen atoms has been directly estimated from the spectroscopic data. The relative populations of the basic building blocks and the average number of O atoms around Te have been estimated for a wide temperature range directly from the Raman spectra, implying a gradual transformation of TeO{sub 4/2} to TeO{sub 2/2}(= O) trigonal pyramid units. The results are discussed in the context of the current phenomenological and theoretical status of the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Theoretical prediction of the band offsets at the ZnO/anatase TiO{sub 2} and GaN/ZnO heterojunctions using the self-consistent ab initio DFT/GGA-1/2 method

The band offsets of the ZnO/anatase TiO{sub 2} and GaN/ZnO heterojunctions are calculated using the density functional theory/generalized gradient approximation (DFT/GGA)-1/2 method, which takes into account the self-energy corrections and can give an approximate description to the quasiparticle characteristics of the electronic structure of semiconductors. We present the results of the ionization potential (IP)-based and interfacial offset-based band alignments. In the interfacial offset-based band alignment, to get the natural band offset, we use the surface calculations to estimate the change of reference level due to the interfacial strain. Based on the interface models and GGA-1/2 calculations, we find that the valence band maximum and conduction band minimum of ZnO, respectively, lie 0.64 eV and 0.57 eV above those of anatase TiO{sub 2}, while lie 0.84 eV and 1.09 eV below those of GaN, which agree well with the experimental data. However, a large discrepancy exists between the IP-based band offset and the calculated natural band offset, the mechanism of which is discussed. Our results clarify band alignment of the ZnO/anatase TiO{sub 2} heterojunction and show good agreement with the GW calculations for the GaN/ZnO heterojunction.

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

Light and Strange Vector Resonances from Lattice QCD at Physical Quark Masses

We present the first ab initio calculation at physical quark masses of scattering amplitudes describing the lightest pseudoscalar mesons interacting via the strong force in the vector channel. Using lattice quantum chromodynamics, we postdict the defining parameters for two short-lived resonances, the ρ(770) and K*(892) which manifest as complex energy poles in ππ and Kπ scattering amplitudes, respectively. The calculation proceeds by first computing the finite-volume energy spectrum of the two-hadron systems and then determining the amplitudes from the energies using the Lüscher formalism. The error budget includes a data-driven systematic error, obtained by scanning possible fit ranges and fit models to extract the spectrum from Euclidean correlators, as well as the scattering amplitudes from the latter. The final results, obtained by analytically continuing multiple parametrizations into the complex energy plane, are M ρ = 796(5)(50)MeV, Γ ρ = 192(10)(31) MeV, M K* = 893(2)(54) MeV, and Γ K = 51(2)(11) MeV, where the subscript indicates the resonance and M and Γ stand for the mass and width, respectively, and where the first bracket indicates the statistical and the second bracket the systematic uncertainty.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2016

Interpretation of the predissociation of the CO Rydberg W {sup 1}Π (v = 1) level

With the goal to interpret the experimental results obtained quite recently by Heays et al. [J. Chem. Phys. 141, 144311 (2014)] on the predissociation of the Rydberg W {sup 1}Π (v = 1) vibrational level of the CO molecule, we report herein ab initio potential energy curves of some of its valence and Rydberg states of both {sup 1}Π and {sup 3}Π symmetry. Our results confirm that the above vibrational level is perturbed by a new electronic {sup 1}Π state not observed until now. They correctly reproduce the linewidths of predissociation of the two interacting levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Investigation of the Fe{sup 3+} centers in perovskite KMgF{sub 3} through a combination of ab initio (density functional theory) and semi-empirical (superposition model) calculations

Analyses of the local crystal and electronic structure in the vicinity of Fe{sup 3+} centers in perovskite KMgF{sub 3} crystal have been carried out in a comprehensive manner. A combination of density functional theory (DFT) and a semi-empirical superposition model (SPM) is used for a complete analysis of all Fe{sup 3+} centers in this study for the first time. Some quantitative information has been derived from the DFT calculations on both the electronic structure and the local geometry around Fe{sup 3+} centers. All of the trigonal (K-vacancy case, K-Li substitution case, and normal trigonal Fe{sup 3+} center case), FeF{sub 5}O cluster, and tetragonal (Mg-vacancy and Mg-Li substitution cases) centers have been taken into account based on the previously suggested experimental and theoretical inferences. The collaboration between the experimental data and the results of both DFT and SPM calculations provides us to understand most probable structural model for Fe{sup 3+} centers in KMgF{sub 3}.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Elucidating the role of reactive nitrogen intermediates in hetero-cyclization during hydrothermal liquefaction of food waste

Hydrothermal liquefaction (HTL) has emerged as a promising strategy for converting abundant, water-rich organic streams into an energy-dense, sustainable, biocrude. Despite major strides in improving oil yields and process intensification, a key underlying challenge persists in relating the composition of the feedstock to the ultimate fate of nitrogen, which is especially important for biocrude quality. To elucidate how nitrogen partitions into the respective gas, aqueous, oil and solid hydrothermal products, food waste was treated under HTL conditions (15 wt% solids, 575 K reaction temperature, and 1 hour reaction time) and elemental, chromatographic and mass spectroscopy analyses were performed on the products to establish dominant product classes and to close mass, carbon, and nitrogen balances. Liquid products (aqueous and biocrude) were found to contain nearly 60% of the nitrogen, with a majority of the biocrude-phase nitrogen in the form of amides. Ab initio thermodynamic and kinetic simulations on model reactants were used to evaluate potential reaction pathways involving reactive nitrogen intermediates. A subsequent kinetic model was evaluated at reaction temperatures ranging 300–1000 K and for a range of feedstock compositions to identify primary reaction pathways. The Maillard reaction is revealed to be the dominant pathway for converting reactive nitrogen intermediates into observed products, especially those in which nitrogen is present as a heterocyclic aromatic. Subsequent product analysis by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) confirms strong agreement among the experimental data, kinetic model and proposed Maillard pathways.

09 BIOMASS FUELS↗
DOE OSTI2023

Lower-length-scale modeling of chemical additions, corrosion and fission products in select MSR base salts

Molten salts play a crucial role in advancing Generation IV nuclear energy technology, with chloride-based salts like NaCl-UCl 3 garnering significant attention due to their distinctive properties. However, the corrosive nature of molten salts causes the dissolution of chromium (Cr), leading to the formation of CrCl 2 and CrCl 3 species in molten chlorides. Moreover, the radioactive decay of nuclear fuel gives rise to fission products, including Cs, Sr, and I chlorides. The first part of this report presents a comprehensive study utilizing ab initio molecular dynamics (AIMD) simulations to investigate the properties of eutectic NaCl-UCl 3 molten salt in the presence of corrosion products (CrCl 2 and CrCl 3 ) and fission product (CsCl). The study focuses on essential structural and thermophysical properties such as density, mixing energy, coordination numbers (CN), and Radial Distribution Functions (RDF) of the salts with varying compositions of corrosion products and fission product, covering a range from 0% to 13.5%. The results offer valuable insights into the behavior of corrosion and fission products in uranium-based molten salts, providing essential data that can be used as input to the MTDB-TC and MSTDB-TP property databases being developed by the NEAMS program. Due to their favorable characteristics such as low melting points, high boiling points, and low costs, MgCl 2 +NaCl+KCl (MNK) eutectic salts have recently attracted attention as high-temperature heat transfer fluids. The incorporation of LiCl into MNK salts can further reduce their melting points and increase their specific heat capacities, which is de- sirable for high-temperature heat transfer applications. The second part of this report presents the development and validation of a new shell-model potential for the MgCl 2 +NaCl+KCl+LiCl system, which captures the polarization of Cl anions. The extensive comparison with experimental data and AIMD simulations demonstrates the accuracy and reliability of the potential. Furthermore, using this potential, we elucidate the intricate network structure in MNK eutectic salts that is formed through polyhedron sharing. This research contributes to a fundamental understanding of the atomic structures and thermophysical properties of multi-component molten salts, which is crucial for future development of heat transfer fluids for applications in molten salt reactors.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Emergent Noncentrosymmetry and Piezoelectricity Driven by Oxygen Octahedral Rotations in n = 2 Dion-Jacobson Phase Layer Perovskites

We demonstrate the loss of centrosymmetry via oxygen octahedral rotations in the n = 2 Dion–Jacobson family of layered oxide perovskites, A'LaB 2 O 7 (A' = Rb, Cs; B = Nb, Ta). Ab initio density functional theory calculations predict that all four materials should adopt polar space groups, in contrast to the results of previous experimental studies that have assigned these materials to the centrosymmetric P4/mmm space group. Optical second harmonic generation experiments confirm the presence of a noncentrosymmetric phase at ambient temperature. Piezoresponse force microscopy experiments also show that this phase is piezoelectric. Moreover, to elucidate the symmetry-breaking and assign the appropriate space groups, the crystal structure of CsLaNb 2 O 7 is refined as a function of temperature from synchrotron X-ray diffraction data. Above 550 K, CsLaNb 2 O 7 adopts the previously determined centrosymmetric P4/mmm space group. Between 550 and 350 K, the symmetry is lowered to the noncentrosymmetric space group Amm2. Below 350 K, additional symmetry lowering is observed as peak splitting, but the space group cannot be unambiguously identified.

47 OTHER INSTRUMENTATION↗
NASA NTRS2011

The Vaporization of B2O3(l) to B2O3(g) and B2O2(g)

The vaporization of B2O3 in a reducing environment leads to formation of both B2O3(g) and B2O2(g). While formation of B2O3(g) is well understood, many questions about the formation of B2O2(g) remain. Previous studies using B(s) + B2O3(l) have led to inconsistent thermodynamic data. In this study, it was found that after heating, B(s) and B2O3(l) appear to separate and variations in contact area likely led to the inconsistent vapor pressures of B2O2(g). To circumvent this problem, an activity of boron is fixed with a two-phase mixture of FeB and Fe2B. Both second and third law enthalpies of formation were measured for B2O2(g) and B2O3(g). From these the enthalpies of formation at 298.15 K are calculated to be -479.9 +/- 41.5 kJ/mol for B2O2(g) and -833.4 +/- 13.1 kJ/mol for B2O3(g). Ab initio calculations to determine the enthalpies of formation of B2O2(g) and B2O3(g) were conducted using the W1BD composite method and show good agreement with the experimental values.

Jacobson, Nathan S.↗
NASA NTRS2002

Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters

Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

Water/chemistry↗
NASA NTRSDate not supplied

Ab Initio Electronic Structure Calculations of CNN for CN Excitation Studies

Titan’s atmosphere is composed mostly of N 2 with a small amount of CH 4 , and so, shock layers around craft entering Titan’s atmosphere will contain a variety of molecules formed from H, C, and N atoms, including the cyanogen radical CN. Sensitivity analysis has shown that the radiative heat flux predicted by computational fluid dynamics (CFD) simulations of Titan entry has up to 14% uncertainty due to the rate coefficients for collisional (de)excitation reactions that control the population of CN in its first and second excited states. The red and violet emission bands from CN’s first and second excited states, respectively, are known to be large sources of radiative heat flux on capsules entering Titan’s atmosphere.[2, 3] So, the simulated population of CN in its first and second excited states is very important, but currently has some inherent uncertainty coming from the data for the rate coefficients for reaction 1. The goal of the present project is to provide improved rate coefficient data for these reactions from first principles quantum chemistry calculations. This work reports on preliminary electronic structure calculations generated at a large number of triatomic geometries of interest, which show multiple avoided crossings at collinear arrangements. This suggests that collisional (de)excitation of CN by N atoms is likely to proceed through these geometries.

Eric Geistfeld↗
DOE OSTI2014

Product fine-structure resolved photodissociation dynamics: The A band of H{sub 2}O

The photodissociation dynamics of H{sub 2}O in its first absorption band is investigated on an accurate potential energy surface based on a large number of high-level ab initio points. Several ro-vibrational states of the parent molecule are considered. Different from most previous theoretical studies, the spin-orbit and Λ-doublet populations of the open-shell OH fragment are reported from full-dimensional wave packet calculations. The populations of the two spin-orbit manifolds are in most cases close to the statistical limit, but the Λ-doublet is dominated by the A{sup ″} component, thanks largely to the fast in-plane dissociation of H{sub 2}O(A{sup ~1}A{sup ′′}). Comparisons with experimental data and a Franck-Condon model are generally very good, although some discrepancies exist.

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

Observation of Long-Range Collective Flow in O + O and Ne + Ne Collisions and Implications for Nuclear Structure Studies

The long-range collective flow of particles produced in oxygen-oxygen ( O + O ) and neon-neon ( Ne + Ne ) collisions is measured with the CMS detector at the CERN LHC. The data samples were collected at a center-of-mass energy per nucleon pair of 5.36 TeV, with integrated luminosities of 7 nb - 1 and 0.8 nb - 1 for O + O and Ne + Ne collisions, respectively. Two- and four-particle azimuthal correlations are measured over nearly five units of pseudorapidity. Significant elliptic ( v 2 ) and triangular ( v 3 ) flow harmonics are observed in both systems. The ratios of v n coefficients between Ne + Ne and O + O collisions suggest sensitivity to the intrinsic nuclear structure of the respective Ne and O ions. Hydrodynamic models with ab initio nuclear structure inputs qualitatively reproduce the collision-overlap dependence of both the v n values and the Ne + Ne to O + O ratios. These measurements provide new constraints when modeling the interplay of nuclear structure and collective dynamics in collisions of O 16 and Ne 20 ions, respectively.

Hayrapetyan, Aram [Yerevan Phys. Inst.]↗
DOE OSTI2018

Relativistic effects in ab initio electron-nucleus scattering

The electromagnetic responses obtained from Green's function Monte Carlo (GFMC) calculations are based on realistic treatments of nuclear interactions and currents. The main limitations of this method comes from its nonrelativistic nature and its computational cost, the latter hampering the direct evaluation of the inclusive cross sections as measured by experiments. We extend the applicability of GFMC in the quasielastic region to intermediate momentum transfers by performing the calculations in a reference frame that minimizes nucleon momenta. Additional relativistic effects in the kinematics are accounted for employing the two-fragment model. In addition, we developed a novel algorithm, based on the concept of first-kind scaling, to compute the inclusive electromagnetic cross section of 4 He through an accurate and reliable interpolation of the response functions. A very good agreement is obtained between theoretical and experimental cross sections for a variety of kinematical setups. Finally, this offers a promising prospect for the data analysis of neutrino-oscillation experiments that requires an accurate description of nuclear dynamics in which relativistic effects are fully accounted for.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗