Tl2Ir2O7: A Pauli Paramagnetic Metal, Proximal to a Metal Insulator Transition
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99 GENERAL AND MISCELLANEOUS↗
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Spectroscopic Investigation of Light-Induced Degradation Paramagnetic Defect in Czochralski Silicon
We report on the electron paramagnetic resonance (EPR) spectra of Cz and FZ Si in different stages of light-induced degradation. Firstly, we show that the paramagnetic signal at low temperature (10K) is dependent on the state of light-induced degradation performed at room temperature and on the sample doping. The light-degraded state in p-Cz Si shows strong, sharp paramagnetic defect signatures compared to samples in the annealed state. When an excitation light is applied during the EPR measurement, additional structures appear in the spectra. In contrast, the wide EPR active signature related to boron interaction with lattice, is present in the annealed state but diminishes after light exposure. Finally, we show that the degraded paramagnetic signal returns when annealed samples are exposed to ambient light. We suggest that these changes in the electron paramagnetic resonance spectra is related to the boron-oxygen defect that causes light-induced degradation.
41 EE - Solar Energy Technologies Office (EE-4S)↗
Local positional and spin symmetry breaking as a source of magnetism and insulation in paramagnetic EuTi O 3
Here we consider theoretically the paramagnetic phases of EuTiO 3 that represent configurations created by two sets of microscopic degrees of freedom (m-DOFs): positional symmetry breaking due to octahedral rotations and magnetic symmetry breaking due to spin disorder. The effect of these sets of m-DOFs on the electronic structure and properties of the para phases is assessed by considering sufficiently large (super) cells with the required nominal global average symmetry, allowing, however, the $\mathcal{local}$ positional and magnetic symmetries to be lowered. We find that tendencies for local symmetry breaking can be monitored by following total energy lowering in mean-fieldlike density-functional theory, without recourse for strong correlation effects. While most nominally cubic ABO 3 perovskites are known for their symmetry breaking due to the B-atom sublattice, the case of f-electron magnetism in EuTiO 3 is associated with A-sublattice symmetry breaking and its coupling to structural distortions. We find that (i) paramagnetic $\mathcal{cubic}$ EuTiO 3 has an intrinsic tendency for both magnetic and positional symmetry breaking, while paramagnetic $\mathcal{tetragonal}$ EuTiO 3 has only magnetic symmetry lowering and no noticeable positional symmetry lowering with respect to low-temperature antiferromagnetic tetragonal phase. (ii) Properly modeled paramagnetic tetragonal and cubic EuTiO 3 have a nonzero local magnetic moment on each Eu ion, consistent with the experimental observations of local magnetism in the para phases of EuTiO 3 significantly above the Néel temperature. Interestingly, (iii) the local positional distortion modes in the short-range ordered para phases are inherited from the long-range ordered low-temperature antiferromagnetic ground-state phase.
36 MATERIALS SCIENCE↗
C-Term magnetic circular dichroism (MCD) spectroscopy in paramagnetic transition metal and f-element organometallic chemistry
Magnetic circular dichroism (MCD) spectroscopy is a powerful experiment used to probe the electronic structure and bonding in paramagnetic metal-based complexes. While C-term MCD spectroscopy has been utilized in many areas of chemistry, it has been underutilized in studying paramagnetic organometallic transition metal and f-element complexes. From the analysis of isolated organometallic complexes to the study of in situ generated species, MCD can provide information regarding ligand interactions, oxidation and spin state, and geometry and coordination environment of paramagnetic species. The pratical aspects of this technique, such as air-free sample preparation and cryogenic experimental temperatures, allow for the study of highly unstable species, something that is often difficult with other spectroscopic techniques. This perspective highlights MCD studies of both transition metal and f-element organometallic complexes, including in situ generated reactive intermediates, to demonstrate the utility of this technique in probing electronic structure, bonding and mechanism in paramagnetic organometallic chemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sensitivity of EDM experiments in paramagnetic atoms and molecules to hadronic CP violation
Experiments searching for the electric dipole moment (EDM) of the electron d e utilize atomic/molecular states with one or more uncompensated electron spins, and these paramagnetic systems have recently achieved remarkable sensitivity to d e . If the source of CP violation resides entirely in the hadronic sector, the two-photon exchange processes between electrons and the nucleus induce CP-odd semileptonic interactions, parametrised by the Wilson coefficient C SP , and provide the dominant source of EDMs in paramagnetic systems instead of d e . We evaluate the C SP coefficients induced by the leading hadronic sources of CP violation, namely nucleon EDMs and CP-odd pion-nucleon couplings, by calculating the nucleon-number-enhanced CP-odd nuclear scalar polarisability, employing chiral perturbation theory at the nucleon level and the Fermi-gas model for the nucleus. This allows us to translate the ACME EDM limits from paramagnetic ThO into novel independent constraints on the QCD theta term |$\bar θ$| < 3 × 10 –8 , proton EDM |d p | < 2 × 10 –23 e cm, isoscalar CP-odd pion-nucleon coupling |$\bar g$$^{(1)}_{πNN}$| < 4 × 10 –10 , and color EDMs of quarks |$\tilde d$ u -$\tilde $d d | < 2 × 10 –24 cm. We note that further experimental progress with EDM experiments in paramagnetic systems may allow them to rival the sensitivity of EDM experiments with neutrons and diamagnetic atoms to these quantities.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Rise and fall of Mott insulating gaps in YNiO 3 paramagnets as a reflection of symmetry breaking and remaking
The YNiO 3 nickelate is a paradigm d-electron oxide that manifests the intriguing temperature-mediated sequence of three phases transitions from (i) magnetically ordered insulator to (ii) paramagnetic (PM) insulator and then to (iii) PM metal. Such phenomena raised the question of the nature of the association of magnetism and structural symmetry breaking with the appearance in (i) and (ii) and disappearance in (iii) of insulating band gaps. It is demonstrated here that first-principles mean-field–like density-functional theory (DFT), driven by molecular dynamics temperature evolution, can describe not only the origin of the magnetically long-range ordered insulating phase (i), but also the creation of an insulating paramagnet (ii) that lacks spin- long-range order, and of a metallic paramagnet (iii) as temperature rises. This approach provides the patterns of structural and magnetic symmetry breaking at different temperatures, in parallel with band gaps obtained when the evolving geometries are used as input to DFT electronic band-structure calculations. This disentangles the complex interplay among spin, charge, and orbital degrees of freedom. Analysis shows that the success in describing the rise and fall of the insulating band gaps along the phase transition sequence is enabled by allowing sufficient flexibility in describing diverse local structural and magnetic motifs as input to DFT. This entails the use of sufficiently large supercells that allow expressing structural disproportionation of octahedra, as well as a description of PM phases as a distribution of local magnetic moments (rather than using a single averaged moment). It appears that the historic dismissal of mean-field–like DFT as being unable to describe such Mott-like transitions was premature, as it was based on consideration of averaged crystallographic unit cells, a description that washes out local symmetry-breaking motifs. The magnetically ordered insulating YNiO 3 phase (i) and the PM insulating phase (ii) result in DFT from allowing symmetry breaking, evident already by considering the athermal internal energy. In contrast, the PM metallic phase (iii) is formed thermally by smearing out thus weakening symmetry breaking. Analysis of snapshots of the different forms of structural vs magnetic symmetry breaking shows that only the loss of the polymorphous distribution of magnetic moments existing in (ii) causes the fall of the band gap, resulting in the metallic state in (iii). Finally, the interesting conclusion is that such a description of the rise [in phases (i) and (ii)] and fall [in phase (iii)] of the insulating gap does not rely on the traditional Mott-like strong correlation understanding, but on breaking and remaking of magnetic and structural symmetries reflected in energy lowering.
36 MATERIALS SCIENCE↗
Spin Seebeck effect at low temperatures in the nominally paramagnetic insulating state of vanadium dioxide
The low temperature monoclinic, insulating phase of vanadium dioxide is ordinarily considered nonmagnetic, with dimerized vanadium atoms forming spin singlets, though paramagnetic response is seen at low temperatures. Here, we find a nonlocal spin Seebeck signal in VO 2 films that appears below 30 K and that increases with a decrease in temperature. The spin Seebeck response has a nonhysteretic dependence on the in-plane external magnetic field. This paramagnetic spin Seebeck response is discussed in terms of prior findings on paramagnetic spin Seebeck effects and expected magnetic excitations of the monoclinic ground state.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Coexisting paramagnetic spins and long-range magnetic order in Ba4(Ru0.92Ir0.08)3O10
We investigate the effect of dilute Ir substitution on the magnetism of the trimer-based ruthenate Ba4Ru3O10 using neutron diffraction, magnetic susceptibility measurements, first-principles calculations, and atomistic simulations. Neutron diffraction shows that Ir doping preserves the zigzag antiferromagnetic structure and the ordered-moment magnitude of the parent compound, in which the moments reside exclusively on the two outer Ru(2) sites of each Ru3O12 trimer, while the central Ru(1) site remains nonmagnetic. The Néel temperature is reduced from ∼105 to 84.0(1) K upon 8% Ir substitution, while magnetic susceptibility reveals a pronounced low-temperature Curie-like upturn, indicating the coexistence of paramagnetic spins with long-range antiferromagnetic order. Density-functional calculations show that Ir preferentially occupies the central Ru(1) site, which disrupts the exchange pathways of the affected Ru3O12 trimer state. Atomistic simulations incorporating this paramagnetic dilution reproduce the suppressed ordering temperature and the coexistence of ordered and paramagnetic components.
Islam, Farhan [Ames Laboratory]↗
Dilute Paramagnetism and Non-Trivial Topology in Quasicrystal Approximant Fe4Al13
A very fundamental property of both weakly and strongly interacting materials is the nature of their magnetic response. In this work, we detail the growth of crystals of the quasicrystal approximant Fe4Al13 with an Al flux solvent method. We characterize our samples using electrical transport and heat capacity, yielding results consistent with a simple non-magnetic metal. However, magnetization measurements portray an extremely unusual response for a dilute paramagnet and do not exhibit the characteristic Curie behavior expected for a weakly interacting material at high temperature. Electronic structure calculations confirm metallic behavior but also indicate that each isolated band near the Fermi energy hosts non-trivial topologies, including strong, weak, and nodal components, with resultant topological surface states distinguishable from bulk states on the (001) surface. With half-filled flat bands apparent in the calculation, but an absence of long-range magnetic order, the unusual quasi-paramagnetic response suggests the dilute paramagnetic behavior in this quasicrystal approximant is surprising and may serve as a test of the fundamental assumptions that are taken for granted for the magnetic response of weakly interacting systems.
Avers, Keenan E. (ORCID:0000000223441939)↗
Investigating Cu-Site Doped Cu–Sb–S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy
Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu–Cu spin exchange or spin–lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Correlating Protein Dynamics and Catalytic Activity of a Model Hydrogenase Using Paramagnetic and Biological Nuclear Magnetic Resonance Spectroscopy
Rational catalyst design remains a significant challenge, with electronic structure, steric, and electrostatic effects known to contribute to activity. Recently, dynamics has been recognized as another factor that impacts catalysis, though identifying and predicting these effects has remained out of reach. Nickel-substituted rubredoxin (NiRd), a protein-based mimic of a hydrogenase enzyme, serves as a model catalytic system in which dynamics can be systematically investigated with respect to activity. While over 30 secondary-sphere mutants of NiRd have been shown to be catalytically active, no significant correlation was observed between the rates and catalytic overpotential or electronic structure, prompting questions about the protein-derived factors that modulate activity. Here, in this work, NMR spectroscopy was used to investigate the roles of substrate accessibility, protein dynamics, and protein stability in controlling catalysis. Significant paramagnetic effects from the nickel center (S = 1) isolate the methylene proton resonances of the metal-coordinating cysteine residues. The sensitivity of resonance positions and linewidths to local environment offers an opportunity to study dynamical molecular changes around the metal center with high resolution. Machine learning algorithms were employed to identify correlations between the catalytic activity and the paramagnetic NMR spectra. These analyses revealed spectroscopic features of specific cysteine protons that report on catalytic overpotential and increased turnover rates, which are further supported by the results obtained using high-field NMR techniques. Collectively, these studies indicate the potential for multifrequency NMR techniques to resolve key contributors to catalytic activity and highlight the importance of local and outer-sphere dynamics.
Protein Engineering↗
Initial-state preparation effects in time-resolved electron paramagnetic resonance experiments
In this paper, we explain a recent experimental observation that the time-resolved electron paramagnetic resonance spectra of an organic molecule for optical excitation within a highly absorbing region of the molecule has similar intensities to the spectra for optical excitation in a nonabsorbing region [D. L. Meyer et al., J. Phys. Chem. Lett. 8, 1677 (2017)]. We demonstrate that this phenomenon is due to an initial-state preparation effect of photoexcitation that leads to similar initial populations of triplet states for both optical excitation regions. Due to the low intersystem crossing rates, the initial triplet populations are not perturbed on the time scale of the experiment, so they determine the relative intensities of the paramagnetic resonance spectra. The effect is surprising given the weak spin-orbit interactions of organic molecules. Such initial-state preparation effects are likely to occur in systems where the intersystem crossing time scales are long compared to the time scale of the experiment.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oscillating paramagnetic Meissner effect and Berezinskii-Kosterlitz-Thouless transition in underdoped Bi2Sr2CaCu2O8+δ
ABSTRACT Superconducting phase transitions in two dimensions lie beyond the description of the Ginzburg-Landau symmetry-breaking paradigm for three-dimensional superconductors. They are Berezinskii-Kosterlitz-Thouless (BKT) transitions of paired-electron condensate driven by the unbinding of topological excitations, i.e. vortices. The recently discovered monolayers of layered high-transition-temperature (${{{T}}}_{{\rm C}}$) cuprate superconductor Bi2Sr2CaCu2O8+δ (Bi2212) meant that this 2D superconductor promised to be ideal for the study of unconventional superconductivity. But inhomogeneity posed challenges for distinguishing BKT physics from charge correlations in this material. Here, we utilize the phase sensitivity of scanning superconducting quantum interference device microscopy susceptometry to image the local magnetic response of underdoped Bi2212 from the monolayer to the bulk throughout its phase transition. The monolayer segregates into domains with independent phases at elevated temperatures below ${{{T}}}_{{\rm C}}$. Within a single domain, we find that the susceptibility oscillates with flux between diamagnetism and paramagnetism in a Fraunhofer-like pattern up to ${{{T}}}_{{\rm C}}$. The finite modulation period, as well as the broadening of the peaks when approaching ${{{T}}}_{{\rm C}}$ from below, suggests well-defined vortices that are increasingly screened by the dissociation of vortex-antivortex plasma through a BKT transition. In the multilayers, the susceptibility oscillation differs in a small temperature regime below ${{{T}}}_{{\rm C}}$, consistent with a dimensional crossover led by interlayer coupling. Serving as strong evidence for BKT transition in the bulk, we observe a sharp jump in phase stiffness and paramagnetism at small fields just below ${{{T}}}_{{\rm C}}$. These results unify the superconducting phase transitions from the monolayer to the bulk underdoped Bi2212, and can be collectively referred to as the BKT transition with interlayer coupling.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Paramagnetic electronic structure of CrSBr: Comparison between ab initio G W theory and angle-resolved photoemission spectroscopy
Here, we explore the electronic structure of paramagnetic CrSBr by comparative first-principles calculations and angle-resolved photoemission spectroscopy. We theoretically approximate the paramagnetic phase using a supercell hosting spin configurations with broken long-range order and applying quasiparticle self-consistent GW theory, without and with the inclusion of excitonic vertex corrections to the screened Coulomb interaction (QS GW and QS $G\widehat{W}$, respectively). Comparing the quasiparticle band-structure calculations to angle-resolved photoemission data collected at 200 K results in excellent agreement. This allows us to qualitatively explain the significant broadening of some bands as arising from the broken magnetic long-range order and/or electronic dispersion perpendicular to the quasi-two-dimensional layers of the crystal structure. The experimental band gap at 200 K is found to be at least 1.51 eV at 200 K. At lower temperature, no photoemission data can be collected as a result of charging effects, pointing towards a significantly larger gap, which is consistent with the calculated band gap of approximately 2.1 eV.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Enhanced detection of paramagnetic fluorine-19 magnetic resonance imaging agents using zero echo time sequence and compressed sensing
Fluorine-19 ( 19 F) magnetic resonance imaging (MRI) is an emerging technique offering specific detection of labeled cells in vivo. Lengthy acquisition times and modest signal-to-noise ratio (SNR) makes three-dimensional spin-density–weighted 19 F imaging challenging. Recent advances in tracer paramagnetic metallo-perfluorocarbon (MPFC) nanoemulsion probes have shown multifold SNR improvements due to an accelerated 19 F T 1 relaxation rate and a commensurate gain in imaging speed and averages. However, 19 F T 2 -reduction and increased linewidth limit the amount of metal additive in MPFC probes, thus constraining the ultimate SNR. To overcome these barriers, we describe a compressed sampling (CS) scheme, implemented using a “zero” echo time (ZTE) sequence, with data reconstructed via a sparsity-promoting algorithm. Our CS-ZTE scheme acquires k-space data using an undersampled spherical radial pattern and signal averaging. Image reconstruction employs off-the-shelf sparse solvers to solve a joint total variation and -norm regularized least square problem. To evaluate CS-ZTE, we performed simulations and acquired 19 F MRI data at 11.7 T in phantoms and mice receiving MPFC-labeled dendritic cells. For MPFC-labeled cells in vivo, we show SNR gains of ~6.3 × with 8-fold undersampling. We show that this enhancement is due to three mechanisms including undersampling and commensurate increase in signal averaging in a fixed scan time, denoising attributes from the CS algorithm, and paramagnetic reduction of T 1 . Importantly, 19 F image intensity analyses yield accurate estimates of absolute quantification of 19 F spins. Overall, the CS-ZTE method using MPFC probes achieves ultrafast imaging, a substantial boost in detection sensitivity, accurate 19 F spin quantification, and minimal image artifacts.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Density functional thermodynamic description of spin, phonon and displacement degrees of freedom in antiferromagnetic-to-paramagnetic phase transition in YNiO 3
This work herein demonstrates a direct density functional description of the finite-temperature thermodynamic properties of solids exhibiting phase transitions through positional and spin symmetry breaking degrees of freedom. A classic example addressed here is the rare-earth (R) nickelates RNiO 3 where the ground state is characterized by crystallographic and magnetic (e.g., antiferromagnetic) long-range order (LRO), whereas the higher temperature paramagnetic phase manifests a range of local spin and positional symmetry breaking motifs with short-range order (SRO). Unlike time-dependent simulations of spin and positional degrees of freedom, in the present work, phases are described via a superposition of static configurations constructed by populating a periodic base lattice supercell allowing for the formation of energy lowing distribution of positional and spin local motifs. The thermal populations of the configurations in such a superposition phase are obtained from the energy-minimized Density Functional Theory (DFT)-calculated partition functions at different temperatures. This approach offers flexible inclusion of different physical contributions to the free energy, such as elastic, electronic and phonon free energies, all obtained from the same underlying DFT total energy calculations of periodic structures. The thermodynamic and magnetic properties of both LRO and SRO crystallographic and spin phases, including antiferromagnetic (AFM) to paramagnetic (PM) Néel phase transition in YNiO3 are studied. Including spin and phonon contributions, we find a DFT-calculated Néel temperature to be 144 K in satisfactory agreement with the experimental value of 145 K; whereas omitting the phonon contribution, one obtains a Néel temperature of 81 K. We present phonon contributions to the DFT-calculated temperature-dependent SRO, heat capacities, and the polymorphous distribution of nonzero local magnetic moments in the PM phase. This approach thus extends to finite temperatures the symmetry-broken DFT description of both the AFM and PM phases, demonstrating that a thermodynamic superposition approach based on symmetry broken configurations evaluated by a mean-field like DFT is sufficient to obtain a consistent description of the thermal physics of the AFM, PM phases and their interconversion in 3d oxides illustrated by YNiO 3 .
36 MATERIALS SCIENCE↗
Spin diffusion in the Phosphorus-31 NMR relaxation in a layered crystalline α-Sn(IV) phosphate contaminated by paramagnetic impurities
The study of a layered crystalline Sn(IV) phosphate by solid-state NMR has demonstrated that the 31 P T 1 relaxation of phosphate groups, dependent on spinning rate is completely controlled by the limited spin diffusion to paramagnetic ions found by EPR. The spin-diffusion constant, D(SD), was estimated as 2.04 10 –14 cm 2 s –1 . Finally, the conclusion was supported by the 31 P T 1 time measurements in zirconium phosphate 1–1, also showing paramagnetic ions and in diamagnetic compound (NH 4 ) 2 HPO 4 .
1H MAS NMR↗
Observation of paramagnetic spin-degeneracy lifting in EuZn 2 Sb 2
Taken together, time-reversal and spatial inversion symmetries impose a twofold spin degeneracy of the electronic states in crystals. In centrosymmetric materials, this degeneracy can be lifted by introducing magnetism, either via an externally applied field or through internal magnetization. However, a correlated alignment of spins, even in the paramagnetic phase, can lift the spin degeneracy of electronic states. Here, we report an in-depth study of the electronic band structure of the Eu-ternary pnictide EuZn 2 Sb 2 through a combination of high-resolution angle-resolved photoemission spectroscopy measurements and first-principles calculations. An analysis of the photoemission line shapes over a range of incident photon energies and sample temperatures is shown to reveal the presence of band spin-degeneracy lifting in the paramagnetic phase. Our angle-resolved photoemission spectroscopy results are in good agreement with theoretical ferromagnetic-phase calculations, which indicates the importance of ferromagnetic fluctuations in the system. Through our calculations, we predict that spin-polarized bands in EuZn 2 Sb 2 generate a single pair of Weyl nodes. Our observation of band splittingin EuZn 2 Sb 2 provides a key step toward realizing time-reversal symmetry breaking physics in the absence of long-range magnetic order.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗