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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Relativistic density functional theory in the full potential linear muffin tin orbital method

In this write-up, we have outlined the general methodology for treating relativity in the FP-LMTO method. The Schrodinger equation is insufficient for describing the physics of heavy elements because it leaves out any relativistic effects. Therefore DFT based on the Schrodinger equation is not sufficient for studying heavy materials. It is, however, possible to incorporate all of the effects of relativity in DFT if starting with a reformulation of the Hohenberg-Kohn theorem that proceeds from the Dirac equation, rather than the Schrodinger equation. The corresponding theorem in relativistic density functional theory (RDFT) shows that the ground-state density of the system is a functional of not only the charge density as in Schrodinger-based DFT, but also of the current density. This leads to a more elaborate procedure in practice when solving the Dirac-Kohn-Sham equations, the relativistic analogs of the Kohn-Sham equations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Connecting relativistic density functional theory to microscopic calculations

The development of systematic effective field theories (EFTs) for nuclear forces and advances in solving the nuclear many-body problem have greatly improved our understanding of dense nuclear matter and the structure of finite nuclei. For global nuclear calculations, density functional theories (DFTs) have been developed to reduce the complexity and computational cost required in describing nuclear systems. However, DFT often makes approximations and assumptions about terms included in the functional, which may introduce systematic uncertainties compared to microscopic calculations using EFTs. In this work, we investigate possible avenues of improving nuclear DFT using nonlinear relativistic mean-field (RMF) theory. We explore the impact of RMF model extensions by fitting the nonlinear RMF model to predictions of nuclear matter and selected closed-shell nuclei using four successful chiral EFT Hamiltonians. We find that these model extensions are impactful and important in capturing the physics present within chiral Hamiltonians, particularly for charge radii and neutron skins of closed-shell nuclei. However, there are additional effects that are not captured within the RMF model, particularly within the isoscalar sector of RMF theory. Additional model extensions and the reliability of the nonlinear RMF model are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Elimination of the linearization error in APW/LAPW basis set: Dirac-Kohn-Sham equations

Here, a detailed account of the implementation of equations of the relativistic density functional theory (RDFT) using basis sets of APW/LAPW type with flexible extensions provided by local orbitals is given. Earlier discoveries of the importance of the high derivative local orbital (HDLO) extension of the APW/LAPW basis set for enhancing the accuracy of DFT calculations are confirmed using a fully relativistic approach and α – U as an example. High energy local orbitals (HELO's), however indispensable for GW calculations, are considerably less efficient in enhancing the accuracy of DFT applications. It is shown that a simplified approach to the relativistic effects, namely considering them only inside the muffin-tin (MT) spheres, produces basically identical results (as compared to fully relativistic approach) for the electronic free energy of the five materials considered in this work. By comparing the effect of the simplified approach on the electronic free energy with its effect on the electronic kinetic energy we conclude that the insensitivity of the free energy to the way we describe the relativistic effects in the interstitial region is related to the variational property of this quantity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

A comprehensive ab initio study of periodic actinide–ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete active-space (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3– , [An(CN) 6 ] 3– , [An(NCS) 6 ] 3– , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3– , and [An(HOPO)] – series of actinide (An = U–Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin–orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted “breaks” in chemical trends. As a result, bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.

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

First principles free energy model with dynamic magnetism for δ -plutonium

We present an ab initio free energy model derived from a fully relativistic density functional theory (DFT) electronic structure with dynamic magnetism for δ -plutonium (face-centered cubic, fcc). The DFT model is extended with orbital-orbital interaction in a parameter free orbital polarization (OP) mechanism consistent with previous modeling of plutonium. Gibbs free energy is built from components associated with the temperature dependence of the electronic structure and the corresponding electronic entropy, lattice vibrations within an anharmonic lattice dynamics model, and dynamical fluctuations of the magnetization density, i.e. magnetic fluctuations. The fluctuation model consists of transverse and longitudinal modes driven by temperature induced excitations of the DFT + OP electronic structure. The ab initio model thus incorporates fluctuating states beyond the electronic ground state. Thanks to the dynamic magnetism, the theory predicts excellent thermodynamic properties and a Gibbs free energy in accord with CALPHAD and semi-empirical modeling developed from the thermodynamic observables. The magnetic fluctuations further explain anomalous behaviors of the thermal expansion in plutonium. Specifically, a thermal expansion for the δ -plutonium system turning from positive to negative at temperatures above room temperature, a tendency for gallium to reduce and remove the negative thermal expansion depending on composition, and a positive thermal expansion for the high temperature ϵ phase.

dynamic↗
DOE OSTI2025

Triaxiality and shape dynamics in 70 Ge

The electromagnetic properties of low-lying states in 70 Ge were investigated via multi-step Coulomb excitation of a 70 Ge beam impinging on a 208 Pb target at the ATLAS facility of the Argonne National Laboratory. A total of 27 transitional elements and six diagonal matrix elements coupling 11 low-lying states, were extracted from the measured cross sections. These were used to calculate reduced transition probabilities, spectroscopic quadrupole moments, and rotational invariant shape parameters, providing enhanced precision and expanding on previous studies. The experimental data were compared within several theoretical frameworks, including the generalized triaxial rotor model, configuration interaction shell-model calculations, and computations within the combined frameworks of relativistic density functional theory and the five-dimensional collective Hamiltonian. The results demonstrate a good agreement with the experimental data and, in conjunction with calculations using a two-state mixing model, support significant triaxiality and strong mixing between the 0$^{+}_{1}$ and 0$^{+}_{2}$ states. This results in the magnitudes of their respective quadrupole deformations [β rms (0$^{+}_{1}$) = 0.228 (3), β rms (0$^{+}_{2}$) = 0.273 (1)] being more similar than previously observed. Furthermore, the implications of these results for understanding the complex shape coexistence phenomena, the role of triaxiality, and shape evolution along the Ge isotopic chain are discussed.

59 ≤ A ≤ 89↗
DOE OSTI2024

Topological material in the III–V family: Heteroepitaxial InBi on InAs

InBi ( 0 0 1 ) is formed epitaxially on InAs ( 1 1 1 ) -A by depositing Bi onto an In-rich surface. Angle-resolved photoemission measurements reveal topological electronic surface states, close to the M ¯ high symmetry point. This demonstrates a heteroepitaxial system entirely in the III–V family with topological electronic properties. InBi shows coexistence of Bi and In surface terminations, in contradiction with other III–V materials. For the Bi termination, the study gives a consistent physical picture of the topological surface electronic structure of InBi ( 0 0 1 ) terminated by a Bi bilayer rather than a surface formed by splitting to a Bi monolayer termination. Theoretical calculations based on relativistic density functional theory and the one-step model of photoemission clarify the relationship between the InBi ( 0 0 1 ) surface termination and the topological surface states, supporting a predominant role of the Bi bilayer termination. Furthermore, a tight-binding model based on this Bi bilayer termination with only Bi–Bi hopping terms, and no Bi–In interaction, gives a deeper insight into the spin texture. Published by the American Physical Society 2024

Nicolaï, Laurent (ORCID:0000000277312673)↗
DOE OSTI2025

A comprehensive approach for elucidating the interplay between 4f n +1 and 4f n 5d 1 configurations in Ln 2+ complexes

Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, C 5 H 4 SiMe 3 (Cp'). The [LnCp' 3 ] complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4f n+1 or 4f n 5d 1 , depending on the specific metal. Standard reduction potentials and 4f n+1 to 4f n 5d 1 promotion energies have been two factors usually considered to rationalize the occurrence of these variable GS configurations, however the driving force behind this phenomenon is still not clear. In this work we present a comprehensive theoretical approach to shed light on this matter using the [LnCp 3 ] - model systems. We begin by calculating 4f n+1 to 4f n 5d 1 promotion energies and successfully correlate them with existing experimental data. Furthermore, we analyze how changes in the GS charge distribution between the Ln ions, LnCp 3 and the reduced [LnCp 3 ] - complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) correlate with experimental trends in redox potentials and the calculated promotion energies. For this purpose, a comprehensive theoretical work that includes relativistic ligand field density functional theory (LFDFT) and relativistic ab initio wavefunction methods was performed. This study will help the rational design of suitable environments to tune the different GS configurations as well as modulating the spectroscopic properties of new Ln 2+ complexes.

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

Weak decays in superheavy nuclei

Superheavy nuclei represent the extreme atoms and nuclides known at the limit of mass and charge. The observed superheavy nuclei are all proton-rich; they decay primarily by emitting 𝛼 particles and by fission with a possible small electron capture (EC) branch. Here, due to the huge atomic numbers and associated relativistic effects, EC decays of superheavy systems are expected to differ from what is known in lighter nuclei. In this letter, using the quantified relativistic nuclear density functional theory and the quasiparticle random-phase approximation with the interaction optimized to experimental EC/𝛽 ± -decay half-lives, and Gamow-Teller resonance energies, we study the EC/𝛽 ± -decays in 𝑍=101–118 nuclei. Both allowed (1 + ) and first-forbidden (0 − ,1 − and 2 − ) transitions are considered. We show that the first-forbidden 1 − transitions dominate the decay rates in almost all studied nuclei. For proton-rich nuclei, EC dominates over 𝛽 + decay. Based on calculations with two relativistic energy density functionals, we identify 45 candidate nuclei in which a competition between weak decays and 𝛼 decay and spontaneous fission is expected.

A ≥ 220↗
DOE OSTI2026

Enhanced antineutrino emission from 𝛽 decay in core-collapse supernovae with self-consistent weak decay rates

Nuclear weak-interaction rates are known to exert a prominent effect in the late stages of stellar collapse. Despite their importance, most studies to date on core-collapse supernovae (CCSNe) have focused primarily on the effects of electron captures, neglecting 𝛽 decay contributions. In this work, we present the first CCSNe simulation incorporating global 𝛽 decay rates from a microscopic theory. These are enabled by a large-scale evaluation of both electron capture and 𝛽 decay rates, obtained self-consistently utilizing the relativistic energy density functional theory and finite-temperature quasiparticle random-phase approximation. Including 𝛽 decay leads to a dramatic enhancement of the pre-bounce antineutrino signal as the antineutrino emissivity increases by more than two orders of magnitude and the luminosity by a factor of 50 relative to thermal emission alone, while the average antineutrino energy increases by over 1 MeV. Furthermore, it is expected that these new rates could help us constrain the model uncertainties related to weak-interaction processes, improving the prediction of antineutrino signal during the final stages of stellar death.

Beta decay↗
DOE OSTI2020

Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. In this work, we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.

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

A closer look at how symmetry constraints and the spin–orbit coupling shape the electronic structure of Bi(111)

Abstract Fully relativistic density-functional-theory calculations of Bi(111) thin films are analyzed to revisit their two metallic surface-states branches. We first contrast these metallic branches with surface states arising at gaps in the valence band opened by the spin–orbit coupling (SOC). We find that the two metallic branches along Γ M ‾ do not overlap with the bulk band at the zone boundary,M. We show that the spin texture observed in such states cannot be traced to the lifting of Kramers’ degeneracy. Instead, we track them to the m j = ± 1 / 2 – m j = ± 3 / 2 SOC splitting, the potential anisotropy for in-plane and out-of-plane states, and the coupling between the opposite surfaces of a slab occurring nearM, which is driven by a spatial redistribution of the four metallic states composing the two metallic branches. Each of these branches appears to be non-degenerate at the tested surface, yet each is degenerate with another state of opposite spin at the other surface. Nevertheless, the four metallic states bear some contribution on both surfaces of the film because of their spatial redistribution nearM. The overlapping among these states nearM, afforded by their spatial redistribution on both surfaces, causes a hybridization that perpetuates the splitting between the two branches, makes the film’s electronic structure thickness dependent nearM, extinguishes the magnetic moment of the metallic states avoiding the magnetic-moment discontinuity atM, and denies the need or expectancy of the metallic branches becoming degenerate atM. We propose that theoppositespin polarization observed for the two metallic branches occurs because the surface atoms retain their covalent bonds and thus cannot afford magnetic polarization. We show that the Rashba-splitting of the metallic states for inversion-asymmetric films does not have a fixed magnitude but can be tuned by changing the perturbation breaking inversion symmetry.

Physics↗
DOE OSTI2023

Gapless spinons and a field-induced soliton gap in the hyperhoneycomb Cu oxalate framework compound [(C 2 H 5 ) 3 NH] 2 Cu 2 (C 2 O 4 ) 3

Here, we report a detailed study of the specific heat and magnetic susceptibility of single crystals of a spin-liquid candidate: the hyperhoneycomb Cu oxalate framework compound [(C 2 H 5 ) 3 NH] 2 Cu 2 (C 2 O 4 ) 3 . The specific heat shows no anomaly associated with a magnetic transition at low temperatures down to T ~ 180 mK in zero magnetic field. We observe a large linear-in-T contribution to the specific heat γT, γ = 98 (1) mJ / mol K 2 , at low temperatures, indicative of the presence of fermionic excitations despite the Mott insulating state. The low-T specific heat is strongly suppressed by applied magnetic fields H, which induce an energy gap, Δ(H), in the spin-excitation spectrum. We use the four-component relativistic density-functional theory (DFT) to calculate the magnetic interactions, including the Dzyaloshinskii-Moriya antisymmetric exchange, which causes an effective staggered field acting on one copper sublattice. The magnitude and field dependence of the field-induced gap, Δ (H) ∝ H 2/3 , are accurately predicted by the soliton mass calculated from the sine-Gordon model of weakly coupled antiferromagnetic Heisenberg chains with all parameters determined by our DFT calculations. Thus our experiment and calculations are entirely consistent with a model of [(C 2 H 5 ) 3 NH] 2 Cu 2 (C 2 O 4 ) 3 in which anisotropic magnetic exchange interactions due to Jahn-Teller distortion cause one copper sublattice to dimerize, leaving a second sublattice of weakly coupled antiferromagnetic chains. We also show that this model quantitatively accounts for the measured temperature-dependent magnetic susceptibility. Thus [(C 2 H 5 ) 3 NH] 2 Cu 2 (C 2 O 4 ) 3 is a canonical example of a one-dimensional spin-1/2 Heisenberg antiferromagnet and not a resonating-valence-bond quantum spin liquid, as previously proposed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Self-consistent microscopic calculations for electron captures on nuclei in core-collapse supernovae

Calculations for electron capture rates on nuclei with atomic numbers between 𝑍 = 20 and 𝑍 = 52 are performed in a self-consistent finite-temperature covariant energy density functional theory within the relativistic quasiparticle random-phase approximation. Electron captures on these nuclei contribute most to reducing the electron fraction during the collapse phase of core-collapse supernovae. The rates include contributions from allowed (Gamow-Teller) and first-forbidden (FF) transitions, and it is shown that the latter become dominant at high stellar densities and temperatures. Temperature-dependent effects such as Pauli unblocking and transitions from thermally excited states are also included. The new rates are implemented in a spherically symmetric one-dimensional simulation of the core-collapse phase. The results indicate that the increase in electron capture rates, due to inclusion of FF transitions, leads to reductions of the electron fraction at nuclear saturation density, the peak neutrino luminosity, and enclosed mass at core bounce. The new rates reaffirm that the most relevant nuclei for the deleptonization situate around the 𝑁 = 50 and 82 shell closures, but, compared to previous simulations, nuclei are less proton rich. Here, the new rates developed in this work are available, and will be of benefit to improve the accuracy of multidimensional supernova simulations.

Electron & muon capture↗
DOE OSTI2021

Unsaturated Sulfur Crown Ethers Can Extract Mercury(II) and Show Promise for Future Copernicium(II) Studies: A Combined Experimental and Computational Study

The unsaturated hexathia-18-crown-6 (UHT18C6) molecule was investigated for the extraction of Hg(II) in HCl and HNO3 media. This extractant can be directly compared to the recently studied saturated hexathia-18-crown-6 (HT18C6). The default conformation of the S lone pairs in UHT18C6 is endodentate, where the pocket of the charge density, according to the crystal structures, is oriented toward the center of the ring, which should allow better extraction for Hg(II) compared to the exodentate HT18C6. Batch study experiments showed that Hg(II) had better extraction at low acid molarity (ca. 99% in HCl and ca. 95% in HNO 3 ), while almost no extraction was observed above 0.4 M HCl and 4 M HNO 3 (<5%). Speciation studies were conducted with the goal of delineating a plausible extraction mechanism. Density functional theory calculations including relativistic effects were carried out on both Hg(II)-encapsulated HT18C6 and UHT18C6 complexes to shed light on the binding strength and the nature of bonding. Our calculations offer insights into the extraction mechanism. In addition to Hg(II), calculations were performed on the hypothetical divalent Cn(II) ion, and showed that HT18C6 and UHT18C6 could extract Cn(II). Finally, the extraction kinetics were explored to assess whether this crown can extract the short-lived Cn(II) species in a future online experiment.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Electron capture of superheavy nuclei with realistic lepton wave functions

The superheavy nuclei push the periodic table of the elements and the chart of the nuclides to their limits, providing a unique laboratory for studies of the electron-nucleus interactions. The most important weak decay mode in known superheavy nuclei is electron capture (EC). In the standard calculations of EC, the lepton wave functions are usually considered in the lowest-order approximation. In this work, we investigate the sensitivity of EC rates on the choice of the electron wave functions by (i) assuming the single-particle approximation for the electron wave functions, and (ii) carrying out Dirac-Hartree-Fock (DHF) calculations. The nuclear response is generated based on the state-of-the-art quasiparticle random phase approximation employing relativistic nuclear energy density functional theory. Here, we show that using the improved lepton wave functions reduces the EC rates up to 40% in the superheavy nucleus oganesson (𝑍=118). Interestingly, because of screening effects, the difference between the EC rates obtained with the DHF and single-particle calculations is fairly small.

Atomic orbital↗
DOE OSTI2026

Large-scale calculations of 𝛽-decay rates and implications for 𝑟-process nucleosynthesis

Nuclear 𝛽 decay is a key element of the astrophysical rapid neutron capture process (𝑟 process). In this work, we present state-of-the-art global 𝛽-decay calculations based on the quantified relativistic nuclear energy density functional theory and the deformed proton-neutron quasiparticle random-phase approximation. Our analysis considers contributions from allowed and first-forbidden transitions. We used two point-coupling functionals with carefully calibrated time-odd terms and isoscalar pairing strength. The new calculations display consistent results for both employed functionals, especially near the neutron drip line, suggesting slower 𝛽 decays past the 𝑁=126 neutron shell closure than in commonly used 𝛽-decay models. The new rates, along with the existing rates based on the recent nonrelativistic global calculations, are found to slow down the synthesis of heavy elements in the 𝑟 process and significantly reduce the contribution of neutron-induced fission.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1995

Electronic structure and the van Hove singularity scenario in high-T(sub c)H(g)Ba2CuO(4+delta) superconductors

The electronic structure and the hole concentrations in the high Tc superconductor HgBa2CuO(4+delta) (delta = O, 1) has been investigated by employing a first principles full potential self-consistent LMTO method with the local density functional theory. The scalar relativistic effects have been considered. The hole concentrations of the Cu-d and O-p(x,y) orbitals are seen to be larger for the HgBaCuO5 system than those of the HgBaCuO4 solid. However, the van Hove singularity (vHs) induced Cu-d and O-p peak which is seen to lie comparatively away and above the Fermi level in the delta = 1 system shifts towards the Fermi level in the delta = 0 system. Thus, the superconducting behavior appears to originate from the occurrence of the vHs peak at the Fermi level. The Fermi surface nesting area in the delta = 0 compound is seen to be larger than in the delta = 1 compound. The calculation reveals that the increase in pressure on the crystal enhances the hole concentrations but without showing any optimum value, On the other hand, the vHs peak approaches to-wards the Fermi level with pressure and crosses the Fermi surface near V/Vo approximately equals 0.625 (V and Vo are the crystal volumes at high and normal pressures, respectively). Our calculated value of the bulk modulus equal to 0.626 Mbar predicts the occurrence of this crossover at about 24 GPa which is in complete agreement with the experimental value. At this pressure the compound has maximum nesting area and self-doped behavior.

Agrawal, Bal K.↗