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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

High-spin states in 60 Cu and implications for states in the mirror nucleus 60 Ga

High-spin states in 60 Cu are investigated on the basis of reaction-channel-selected 𝛾-ray spectroscopy. Data stem from three experiments that used the same fusion-evaporation reaction at similar beam energies. The Gammasphere 𝛾-ray spectrometer was combined with the Microball CsI(Tl) detector array and sets of liquid-scintillator neutron detectors which allowed us to identify and tag on evaporated light charged particles and neutrons, respectively. A level scheme is proposed which comprises more than 300 𝛾-ray transitions connecting more than 100 excited states. Predictions from cranked Nilsson-Strutinsky calculations describe the observed high-spin collective structures in 60 Cu. Predictions of shell-model calculations are probed with a suite of low- to medium-spin states of both parities. Taking into account isospin-symmetry-breaking terms in these calculations, a case study of the yrast line of the weakly bound mirror nucleus 60 Ga is presented.

Rudolph, Dirk [Lund University (Sweden)] (ORCID:00↗
DOE OSTI2025

Understanding the Existence of a Na 2 Dimer in a High-Spin State

The recent observation of a high-spin Na 2 dimer formed on the surface of liquid helium nanodroplets raises some fundamental questions, as the ground state of Na 2 is known to have zero spin. Is it protected against spontaneous dissociation? What is its binding energy and interatomic distance? Is it stable at a higher temperature? Using calculations based on density functional theory (with and without long-range interaction) and coupled cluster methods, CCSD(T), we show that the bonding in the high-spin Na 2 dimer is governed by van der Waals interaction with binding energy (bond length) varying between −0.030 eV (5.108 Å) and −0.192 eV (4.231 Å), depending on the computational method used. Thus, the experimental method used by Kresin and coworkers can be very useful to study larger metastable high-spin clusters such as Li 4 which was predicted in 1985 to have a tetrahedral structure carrying a magnetic moment of 2 μ B , while its ground state is planar and nonmagnetic.

Basis sets↗
DOE OSTI2024

Coexistence of low and high spin states in La 18 Co 28 Pb 3

The electronic structure and magnetic properties of a newly predicted stable ternary compound La 18 ⁢Co 28 ⁢Pb 3 are studied using electronic structure analysis. The ground state of this compound is ferromagnetic, with three positions of nonequivalent magnetic Co atoms. A strong dependence of magnetic properties on volume shows that this system is situated near the point of magnetic instability. The coexistence of high- and low-spin ferromagnetic states as a function of volume near equilibrium was discovered. A corresponding spin tunneling splitting was estimated. The stability of the theoretically predicted magnetic ground state was tested by varying the Hubbard parameter. The thermal spin fluctuations were added to estimate the paramagnetic moment and a Curie temperature. Finally, the necessity of experimental verification of the obtained results is emphasized.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Mechanistic implications of excited high-spin states, spin–spin coupling, and differential [2Fe–2S] + cluster temperature relaxations in the electron-bifurcating NfnABC from Thermococcus sibiricus

Electron bifurcation (EB) is a mechanism of biological energy transduction in which multiple oxidation–reduction (redox) reactions are thermodynamically coupled within a single enzyme, enabling the enzyme to harness the excess free energy from an exergonic process to drive an endergonic process. Because of this unprecedented chemistry, there is interest to translate EB principles to artificial and bioengineered systems, but a hurdle is that knowledge pertaining to the fundamental design principles of EB enzymes remains scarce. Here, we investigated the fundamental physical and electronic properties of electron transfer sites in a spectroscopically uncharacterized member of the BfuABC family of EB enzymes, the NADH-dependent reduced-ferredoxin:NADP + oxidoreductase from Thermococcus sibiricus (Tsi NfnABC). Cryo-EM structures of Tsi NfnABC previously demonstrated that it contains twelve redox cofactors: two flavins (one FAD and one FMN), eight [4Fe–4S] clusters, and two [2Fe–2S] clusters. The FMN, one [4Fe–4S] cluster, and one [2Fe–2S] cluster comprise the bifurcating active site termed the electron-bifurcating flavobicluster (BF-FBC), which is found in all BfuABC family members. By using electron paramagnetic resonance spectroscopy, we identified spectral signatures originating from interactions between the FMN radical and [4Fe–4S] + cluster in the BF-FBC and observed temperature dependent behavior of the BF-FBC's [2Fe–2S] + cluster indicative of moderately slow spin–lattice relaxation. Additionally, we uncovered numerous spectral features corresponding to half-integer, S > ½ spin states of [4Fe–4S] + clusters, including one attributable to the consequences of lysine-ligation of a [4Fe–4S] cluster unique to NfnABC. We contextualize these findings to electron transfer theory and NfnABC's structure. Our insights further the understanding of how enzymes are designed to exert control over electron transfer to conduct thermodynamically challenging reactions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

The computational investigation of the molecular geometries of a pair of manganese(III) spin-crossover complexes is reported. For the geometry of the quintet high-spin state, density functionals significantly overestimate Mn–Namine bond distances, although the geometry for the triplet intermediate-spin state is well described. Here, comparisons with several wave function-based methods demonstrate that this error is due to the limited ability of commonly used density functionals to recover dispersion beyond a certain extent. Among the methods employed for geometry optimization, restricted open-shell Møller–Plesset perturbation theory (MP2) appropriately describes the high-spin geometry but results in a slightly shorter Mn–O distance in both spin states. On the other hand, extended multistate complete active space second-order perturbation theory (XMS-CASPT2) provides a good description of the geometry for the intermediate-spin state but also sufficiently recovers dispersion, performing well for the high-spin state. Despite the fact that the electronic structure of both spin states is dominated by one-electron configuration, XMS-CASPT2 offers a balanced approach, leading to molecular geometries with much better agreement with experiment than MP2 and DFT. A scan along the Mn–N amine bond demonstrates that for these complexes coupled cluster methods (i.e., DLPNO-CCSD(T)) also yield bond distances in agreement with experiment while multiconfiguration pair density functional theory (MC-PDFT) is unable to recover dispersion well enough, analogous to single-reference DFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spin inhibition in γ -decay probabilities for states above S n in Sm and Dy nuclei

When a compound nucleus is formed at an excitation energy above the neutron-separation threshold, it is assumed that its de-excitation will proceed via neutron emission. However, if the excited nucleus is in a high-spin state, but does not have enough excitation energy to conserve angular momentum by either photon emission after neutron emission or relative angular momentum carried off by the neutron, the nucleus will de-excite via γ -emission instead. This effect, the spin inhibition, provides an insight into the structure of the compound nuclei and can aid the understanding of the distribution of the populated spin states in a compound nuclear reaction. In this work, the effects of spin inhibition on the γ-decay probabilities from states in 146,147Sm and 160Dy are presented. For high-spin states above the Sn, spin inhibition is able to suppress neutron emission, and de-excitation via γ -ray emission is observed for states up to 3 MeV above the Sn .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Out-of-equilibrium dynamics of a grid-like Fe( II ) spin crossover dimer triggered by a two-photon excitation

The application of two-photon excitation (TPE) in the study of light-responsive materials holds immense potential due to its deeper penetration and reduced photodamage. Despite these benefits, TPE has been underutilised in the investigation of the photoinduced spin crossover (SCO) phenomenon. Here, we employ TPE to delve into the out-of-equilibrium dynamics of a SCO Fe II dimer of the form [Fe II (HL) 2 ] 2 (BF 4 ) 4 ·2MeCN (HL = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole). Optical transient absorption (OTA) spectroscopy in solution proves that the same dynamics take place under both one-photon excitation (OPE) and TPE. The results show the emergence of the photoinduced high spin state in less than 2 ps and with a lifetime of 147 ns. Time-resolved photocrystallography (TRXRD) reveals a single molecular reorganisation within the first 500 ps following TPE. Additionally, variable temperature single crystal X-ray diffraction (VTSCXRD) and magnetic susceptibility measurements confirm that the thermal transition is silenced by the solvent. While the results of the OTA and TRXRD utilising TPE are intriguing, the high pump fluencies required to excite enough metal centres to the high spin state may impair its practical application. Nonetheless, this study sheds light on the potential of TPE for the investigation of the out-of-equilibrium dynamics of SCO complexes.

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

Characterization of ferredoxins involved in electron transfer pathways for nitrogen fixation implicates differences in electronic structure in tuning 2[4Fe 4S] Fd activity

Ferredoxins (Fds) are small proteins which shuttle electrons to pathways like biological nitrogen fixation. Physical properties tune the reactivity of Fds with different pathways, but knowledge on how these properties can be manipulated to engineer new electron transfer pathways is lacking. Recently, we showed that an evolved strain of Rhodopseudomonas palustris uses a new electron transfer pathway for nitrogen fixation. This pathway involves a variant of the primary Fd of nitrogen fixation in R. palustris, Fer1, in which threonine at position 11 is substituted for isoleucine (Fer1 T11I ). To understand why this substitution in Fer1 enables more efficient electron transfer, we used in vivo and in vitro methods to characterize Fer1 and Fer1 T11I . Electrochemical characterization revealed both Fer1 and Fer1 T11I have similar redox transitions (–480 mV and – 550 mV), indicating the reduction potential was unaffected despite the proximity of T11 to an iron-sulfur (Fe—S) cluster of Fer1. Additionally, disruption of hydrogen bonding around an Fe—S cluster in Fer1 by substituting threonine with alanine (T11A) or valine (T11V) did not increase nitrogenase activity, indicating that disruption of hydrogen bonding does not explain the difference in activity observed for Fer1 T11I . Electron paramagnetic resonance spectroscopy studies revealed key differences in the electronic structure of Fer1 and Fer1 T11I , which indicate changes to the high spin states and/or spin-spin coupling between the Fe—S clusters of Fer1. Finally, our data implicates these electronic structure differences in facilitating electron flow and sets a foundation for further investigations to understand the connection between these properties and intermolecular electron transfer.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Nanoscale Tracking of the High-Temperature Spin-State Transition in LaCoO 3

The high-temperature spin and electronic transitions in LaCoO 3 have recently been leveraged to create neuromorphic (brain-inspired) devices. While these devices have shown the potential for impactful functionality in next-generation computing systems, the nanoscale dynamics of the spin and electronic transitions that underlie their operation are not well understood. Inhomogeneities related to interfaces, electrode contacts, strain, and crystal defects can all affect device performance, making nanoscale characterization of the transitions essential for producing consistent and reliable devices. Here, we demonstrate the first nanoscale in situ measurement of the spin transition in LaCoO 3 at device-relevant temperatures (25–325 °C) over length scales of tens of nanometers using STEM-EELS. This measurement is enabled by an Al 2 O 3 coating, which prevents unwanted reduction of the LaCoO 3 specimen at high temperature and vacuum. The detailed understanding of LaCoO 3 transition dynamics enabled by such measurements will be crucial for optimizing LaCoO 3 -based neuromorphic devices and increasing reliability for real-world application.

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

Correlation between antiferromagnetic and Mott states in spin orbit coupled Sr 2 Ir O 4 : A study of Sr 2 Ir 1 – x M x O 4 ( M = Fe or Co)

Sr 2 IrO 4 is an archetypal spin-orbit-coupled Mott insulator with an antiferromagnetic state below 240 K. Here we report results of our study on single crystals of Sr 2 Ir 1–x Fe x O 4 (0 ≤ x < 0.32) and Sr 2 Ir 1–x Co x O 4 (0 ≤ x < 0.22). Fe doping retains the antiferromagnetic state but simultaneously precipitates an emergent metallic state whereas Co doping causes a rapid collapse of both the antiferromagnetic and Mott states, giving rise to a confined metallic state featuring a pronounced linearity of the basal-plane resistivity up to 700 K. The results indicate tetravalent Fe 4+ (3d 4 ) ions in the intermediate spin state with S = 1 and Co 4+ (3d 5 ) ions in the high spin state with S = 5/2 substituting for Ir 4+ (5d 5 ) ions in Sr 2 IrO 4 , respectively. The effective magnetic moment closely tracks the Néel temperature as doping increases, suggesting that the spin state of the dopant predominately determines the magnetic properties in doped Sr 2 IrO 4 . Furthermore, all relevant properties including charge-carrier density (e.g., 10 28 /m 3 ), Sommerfeld coefficient (e.g., 19 mJ / mole K 2 ), and Wilson ratio (e.g., 2.6) consistently demonstrate an emergent metallic state that is both robust and highly correlated in the two systems, arising from the percolation of bound states and the weakening of structural distortions. Furthermore, this study strongly indicates that the antiferromagnetic and Mott states are correlated in an unconventional manner in Sr 2 IrO 4 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance

A low-coordinate, high spin (S = 3/2) organometallic iron(I) complex is a catalyst for the isomerization of alkenes. A combination of experimental and computational mechanistic studies supports a mechanism in which alkene isomerization occurs by the allyl mechanism. Importantly, while substrate binding occurs on the S = 3/2 surface, oxidative addition to an η 1 -allyl intermediate only occurs on the S = 1/2 surface. In conclusion, since this spin state change is only possible when the alkene substrate is bound, the catalyst has high immunity to typical σ-base poisons due to the antibonding interactions of the high spin state.

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

Observation of collective modes of excitations in 59 Co, 59 Ni, and 61 Co and the influence of the $g_{9/2}$ orbital

High-spin states in 59 Co (Z = 27), 59 Ni (Z = 28), and 61 Co have been populated by the fusion evaporation reactions, 48 Ti( 14 C, p2n ) 59 Co, 48 Ti( 14 C, 3 n ) 59 Ni, and 50 Ti( 14 C, p2n ) 61 Co. The 9 MV tandem accelerator at the John D. Fox Laboratory, Florida State University (FSU) was used to accelerate the 14 C beam and the deexciting γ rays were detected by the FSU detector array consisting of six high-purity germanium (HPGe) clover detectors and three single crystals. Directional correlation of the $γ$ rays deexciting oriented states (DCO ratios) and polarization asymmetry measurements helped to establish spin and parities of the excited states whenever possible. The level scheme of 59 Co has been expanded with the inclusion of positive-parity states up to 31/2 + at around 11 MeV. The 59 Ni positive-parity states known from previous study were verified with modifications to some of the spins and parities. On the other hand, the negative-parity states were extended to 31/2 at an excitation energy of 12 MeV. No new transition was observed for 61 Co, but one of the major bands has been reassigned as consisting of positive-parity states by reason of this study. Importantly, excitations observed within the f 7/2 , p 3/2 , f 5/2 , and p 1/2 orbitals, and also across the N = 40 subshell closure into the g 9/2 orbital was established by comparison with large-scale shell-model calculations for the three nuclei studied.

59 ≤ A ≤ 89↗
DOE OSTI2020

Dispersive optical model analysis of 208 Pb generating a neutron-skin prediction beyond the mean field

In this work, a nonlocal dispersive optical model analysis is carried out for neutrons and protons in 208 Pb. Elastic-scattering angular distributions, total and reaction cross sections, single-particle energies, neutron and proton numbers, the charge distribution, and the binding energy are fitted to extract the neutron and proton self-energies both above and below the Fermi energy. From the single-particle propagator derived from these self-energies, we determine the charge and matter distributions in 208 Pb. The predicted spectroscopic factors are consistent with results from the ($\textit{e,e}'\textit{p}$) reaction and inelastic-electron-scattering data to very high-spin states. Sensible results for the high-momentum content of neutrons and protons are obtained, with protons appearing more correlated, in agreement with experiment and ab initio calculations of asymmetric matter. A neutron skin of 0.25 ± 0.05 fm is deduced. An analysis of several nuclei leads to the conclusion that finite-size effects play a nonnegligible role in the formation of the neutron skin in finite nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗