Pauli Paramagnetism Research Articles

Absence of magnetic order in RuO2: insights from μSR spectroscopy and neutron diffraction

Altermagnets are a novel class of magnetic materials, where magnetic order is staggered both in coordinate and momentum space. The metallic rutile oxide RuO2, long believed to be a textbook Pauli paramagnet, recently emerged as a putative workhorse altermagnet when resonant X-ray and neutron scattering studies reported nonzero magnetic moments and long-range collinear order. While some experiments seem consistent with altermagnetism, magnetic order in RuO2 remains controversial. We show that RuO2 is nonmagnetic, both in bulk and thin film. Muon spectroscopy complemented by density-functional theory finds at most 1.14 × 10−4 μB/Ru in bulk and at most 7.5 × 10−4 μB/Ru in 11 nm epitaxial films, at our spectrometers’ detection limit, and dramatically smaller than previously reported neutron results that were used to rationalize altermagnetic behavior. Our own neutron diffraction measurements on RuO2 single crystals identify multiple scattering as the source for the false signal in earlier studies.

Hard x-ray magnetic circular dichroism under high magnetic field

We describe high-field X-ray magnetic circular dichroism (XMCD) setup developed at the European Synchrotron Radiation Facility beamline ID12, which is dedicated to polarization dependent X-ray absorption spectroscopy in the soft and hard X-ray range from 2 to 15 keV. The static magnetic field up to 17 T is generated by a superconducting solenoid. Performance of the setup is illustrated with three representative studies: metamagnetic transitions in PrCo2Ge2 single crystal, Pauli paramagnetism in uranium monocarbide, and induced magnetism on gold atoms in different environment: MnAu4, UAu4 and a pure gold metal.

Potassium- and Lithium-Ammonia Intercalation into Excitonic Insulator Candidate Ta2NiSe5.

Two new reduced phases derived from the topical excitonic insulator candidate Ta2NiSe5 have been synthesized via the intercalation of lithium and potassium from solutions of the metals in liquid ammonia. Li(NH3)Ta2NiSe5 and KTa2NiSe5 both crystallize in orthorhombic space group Pmnb with the following lattice parameters: a = 3.5175(1) Å, b = 18.7828(7) Å, and c = 15.7520(3) Å and a = 3.50247(3) Å, b = 13.4053(4) Å, and c = 15.7396(2) Å, respectively. They have increased unit cell volumes of 48% and 31%, respectively, relative to that of Ta2NiSe5. Significant rearrangement of the transition metal selenide layers is observed in both intercalates compared to the parent phase. In Li(NH3)Ta2NiSe5, neutron diffraction experiments confirm the location of the light Li, N, and H atoms, and solid-state nuclear magnetic resonance (NMR) experiments show that H, N, and Li each occupy a single environment at ambient temperature on the NMR time scale. Magnetometry data show that both intercalates have increased magnetic susceptibilities relative to that of Ta2NiSe5, consistent with the injection of electrons during intercalation and an enhancement of the Pauli paramagnetism.

Electronic State-Regulated Magnetic Phenomena in Single-Crystal FeSe

In contrast to the observed high-temperature superconductivity in monolayer FeSe/SrTiO3 films, akin to CoSb/SrTiO3, the bulk counterpart, FeSe, does not exhibit superconductivity even under elevated pressure, and its magnetic characteristics remain subject to debate. This investigation delves into the electrical and magnetic attributes, alongside X-ray photoelectron spectroscopy (XPS) analysis, of FeSe mono-crystal. Magnetic and electrical transport assessments indicate that FeSe demonstrates characteristics of a Pauli paramagnetic metal within non-Fermi liquid traits. XPS analysis further reveals that the Fe and Se pair in FeSe exist in a zero-valence state, forming a predominantly metallic-bonded alloy. The Pauli paramagnetism observed in FeSe is ascribed to its itinerant electrons. The comprehension of the electronic states in FeSe mono-crystal not only clarifies its lack of magnetic characteristics but also paves the way for exploring potential high-temperature superconductivity.

Temperature Evolution of Composition, Thermal, Electrical and Magnetic Properties of Ti3C2Tx-MXene.

MXenes are a family of two-dimensional nanomaterials. Titanium carbide MXene (Ti3C2Tx-MXene), reported in 2011, is the first inorganic compound reported among the MXene family. In the present work, we report on the study of the composition and various physical properties of Ti3C2Tx-MXene nanomaterial, as well as their temperature evolution, to consider MXenes for space applications. X-ray diffraction, thermal analysis and mass spectroscopy measurements confirmed the structure and terminating groups of the MXene surface, revealing a predominant single OH layer character. The temperature dependence of the specific heat shows a Debye-like character in the measured range of 2 K-300 K with a linear part below 10 K, characteristic of conduction electrons of metallic materials. The electron density of states (DOS) calculations for Ti3C2OH-MXene reveal a significant DOS value at the Fermi level, with a large slope, confirming its metallic character, which is consistent with the experimental findings. The temperature dependence of electrical resistivity of the MXene samples was tested for a wide temperature range (3 K-350 K) and shows a decrease on lowering temperature with an upturn at low temperatures, where negative magnetoresistance is observed. The magnetoresistance versus field is approximately linear and increases its magnitude with decreasing temperature. The magnetization curves are straight lines with temperature-independent positive slopes, indicating Pauli paramagnetism due to conduction electrons.

Fabrication and properties of lateral Josephson junctions with a RuO2 weak link

Ruthenium dioxide (RuO2) is a metallic rutile oxide with a number of interesting properties. For a long time, it was considered to be a highly conductive normal metal and a Pauli paramagnet. Recently, it was found that the material is antiferromagnetic, with small magnetic moments of the order of 0.05 Bohr magneton and an ordering temperature above 300 K. The presence of magnetic moments should have clear consequences when trying to induce superconductivity in RuO2. We used a selective area chemical vapor deposition method to grow nanostrips of RuO2 on TiO2 substrates. On these nanostrips, superconducting contacts were made of MoGe, and a weak link was fabricated with a Focused Ion Beam. We find that the device behaves as a Josephson junction, including a Fraunhofer-like response to a magnetic field, for distances between the contacts below 70 nm. We estimate the induced singlet coherence length ξ to be about 12 nm, which seems a reasonable number when small magnetic moments are present.

The crystal structures and magnetic properties of YbMg0.75In1.25 and Yb6Mg6.41In5.59

Abstract The quasi-binary system YbMg2-YbIn2 was studied around the equiatomic composition. In contrast to the ordered rare earth (RE) phases REMgIn (ZrNiAl type), ytterbium forms phases with different structures and pronounced Mg/In mixing (M sites). The structures of YbMg0.75In1.25 (CaLiSn type, P3m1, a = 501.95(7), c = 1087.3(2) pm, wR2 = 0.0490, 790 F 2 values, 32 variables) and Yb6Mg6.41In5.59 (Yb6Ir5Ga7 type, P63/mcm, a = 1060.77(14), c = 970.27(16) pm, wR2 = 0.0484, 701 F 2 values, 26 variables) were refined from single-crystal X-ray diffractometer data. YbMg0.75In1.25 is an AlB2 superstructure with a tripling of the subcell. The magnesium and indium atoms form three differently puckered layers of M 6 hexagons. The Yb6Mg6.41In5.59 structure is derived from the hexagonal Laves phase YbMg2 (MgZn2 type, P63/mmc). A klassengleiche symmetry reduction leads to four crystallographically independent M sites for the rows of corner- and face-sharing tetrahedra which allow a composition close to the equiatomic one. The M–M distances in both structures cover the broad range from 289 to 331 pm, comparable to the sums of the covalent radii. Temperature dependent magnetic susceptibility studies of the polycrystalline YbMg0.75In1.25 and Yb12Mg13In11 samples indicate Pauli paramagnetism with room temperature values of 2.8(1) × 10−3 emu mol−1 (YbMg0.75In1.25) and 5.2(1) × 10−3 emu mol−1 (Yb12Mg13In11).

Controlling the Superconductivity of Nb2PdxS5 via Reversible Li Intercalation.

The Nb2PdxS5 (x ≈ 0.74) superconductor with a Tc of 6.5 K is reduced by the intercalation of lithium in ammonia solution or electrochemically to produce an intercalated phase with expanded lattice parameters. The structure expands by 2% in volume and maintains the C2/m symmetry and rigidity due to the PdS4 units linking the layers. Experimental and computational analysis of the chemically synthesized bulk sample shows that Li occupies triangular prismatic sites between the layers with an occupancy of 0.33(4). This level of intercalation suppresses the superconductivity, with the injection of electrons into the metallic system observed to also reduce the Pauli paramagnetism by ∼40% as the bands are filled to a Fermi level with a lower density of states than in the host material. Deintercalation using iodine partially restores the superconductivity, albeit at a lower Tc of ∼5.5 K and with a smaller volume fraction than in fresh Nb2PdxS5. Electrochemical intercalation reproduces the chemical intercalation product at low Li content (<0.4) and also enables greater reduction, but at higher Li contents (≥0.4) accessed by this route, phase separation occurs with the indication that Li occupies another site.

The HfFe2Si2 type silicides ScT 2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy

Abstract The silicides ScT 2Si2 (T = Ru, Rh, Os) were synthesized by arc-melting of the elements and subsequent annealing in sealed silica ampoules. They crystallize with the rarely observed HfFe2Si2 type structure, space group Pbcm. The structures of ScRu2Si2 (a = 761.64(4), b = 730.70(6), c = 521.07(6) pm, wR = 0.0314, 633 F 2 values, 31 variables) and ScOs2Si2 (a = 771.10(8), b = 736.68(7), c = 521.88(5) pm, wR = 0.0479, 623 F 2 values, 31 variables) were refined from single crystal X-ray diffractometer data. The refinements showed small degrees of Ru/Si respectively Os/Si mixing on one 4c site, leading to the refined compositions ScRu1.96(1)Si2.04(1) and ScOs1.91(1)Si2.09(1). The monomeric building units in both structures are two slightly distorted, crystallographically independent RuSi5 respectively OsSi5 square pyramids, which are condensed via common edges. The resulting densely packed [Ru2Si2] and [Os2Si2] networks leave voids for the scandium atoms with coordination number 18: Sc@Si8Ru8Sc2 and Sc@Si8Os8Sc2. Temperature dependent magnetic susceptibility measurements of ScRu2Si2 and ScOs2Si2 indicate Pauli paramagnetism. Solid-state 29Si and 45Sc static and MAS NMR spectroscopy reveal significant Knight shifts and a strong influence of the T/Si mixing on the experimental NMR line shapes. A larger overall 29Si magnetic shift for ScRu2Si2 compared to ScOs2Si2, although with a negative sign for one of the 29Si resonances, suggests stronger paramagnetic effects for ScRu2Si2, in agreement with the magnetic susceptibility measurements.

Electronic state dominated magnetism in CoSb single crystal

Both theoretical calculations and experiments indicate that a monolayer CoSb/SrTiO3 film has high-temperature superconductivity resembling the case of FeSe/SrTiO3. However, no superconductivity was found in the bulk CoSb, even under high pressure. Moreover, the magnetic properties of CoSb have always been controversial. Here, we have studied the electrical property, magnetic property, and X-ray photoelectron spectroscopy (XPS) of CoSb single crystals. Electrical and magnetic transportation measurements reveal that CoSb is a Pauli paramagnetic metal with non-Fermi liquid behavior. The XPS results showed that both Co and Sb in CoSb are in the zero-valence state, and they form an alloy in which the metallic bond is dominant. The Pauli paramagnetism of CoSb originates from its itinerant electrons. Therefore, unveiling the electronic states of CoSb single crystal not only help us understand its magnetic properties, but would also pave the way for searching for the possible high-temperature superconductivity.

Cementite-type Y3Ru

Abstract Single crystals of Y3Ru were obtained as a side product during phase analytical studies of yttrium-rich compounds in the system Y–Ru–Zn. The structure of Y3Ru was refined from single-crystal X-ray diffractometer data: Fe3C type, Pnma, a = 732.51(7), b = 925.61(8), c = 633.66(10) pm, wR = 0.0639, 811 F 2 values, 23 variables. The ruthenium atoms have coordination number 9 in form of a strongly distorted tricapped trigonal yttrium prism with Ru–Y distances ranging from 275–391 pm. The second substructure concerns empty Y6 octahedra (d(Y–Y) = 344–396 pm). Electronic structure calculations show a net charge transfer from yttrium to ruthenium and underpin the essentially covalent Y–Ru bonding. A phase-pure sample of Y3Ru was synthesized from the elements by arc-melting. Temperature-dependent magnetic susceptibility studies of this sample reveal Pauli paramagnetism (3.6(1) × 10−5 emu mol−1 at T = 300 K).

Continuous-wave and pulsed EPR studies of glass-like carbon with high spin concentration: Evidence for triplet states

Glass-like carbons (GLCs) are a large group of disordered carbon materials which have applications in various fields, but not all their properties are well characterized. In particular, they have high concentration of paramagnetic centers (PCs) which are easily observed by electron paramagnetic resonance (EPR). However, an apparently simple EPR spectrum, together with its peculiarities caused by high electrical conductivity, make it difficult to identify the PCs and their origin remains unknown. To resolve these unsettled questions, in this work we use the vacuum Rabi splitting and Rabi oscillations which so far have not been applied to study these materials by the continuous wave (CW) and pulsed EPR. GLC produced by pyrolysis of phenol-formaldehyde resin at 1120 K was studied in the temperature range of 4.3–300 K. Using the Rabi splitting we found conditions for undistorted registration of CW EPR spectra and determined spin concentration (1×1020 spin/g). The temperature dependence of the EPR susceptibility shows the coexistence of Pauli paramagnetism due to conduction electrons and the Curie-type paramagnetism of thermally activated PCs with the activation energy of 5.7 cm-1. These PCs may be excited triplet states, the presence of which is revealed by Rabi oscillations in the pulsed EPR.

Hall effect of RCo2 (R= Er and Lu) compounds

The Hall effect of RCo2 with R = Er and Lu has been studied. LuCo2 is an exchange-enhanced Pauli paramagnet. ErCo2 is ferrimagnetic below TC = 32 K and undergoes a first-order magnetic transition at TC. The Hall resistivity ρxy was measured as a function of the magnetic field B at various temperatures. We estimated the normal (ordinary) Hall coefficient RN and the anomalous Hall coefficient RA from the analyses of the ρxy – B curves and the magnetization curves. For LuCo2, ρxy increases linearly with increasing field and its slope decreases rapidly with increasing temperature below 70 K. This is attributable to strong temperature dependence of RN. The ρxy – B curve of ErCo2 depends on a magnetic state. In the ferrimagnetic state, both RN and RA have positive values, while RN is positive and RA is negative in the paramagnetic state. We calculated RN's of nonmagnetic and ferromagnetic LuCo2 from the energy band structures and compared them with the experimental values. The origin of a sign change in RA of ErCo2 is briefly discussed.

Microwave-Assisted Synthesis of the New Solid-Solution (V1–xCrx)2GaC (0 ≤ x ≤ 1), a Pauli Paramagnet Almost Matching the Stoner Criterion for x = 0.80

MAX phases that exhibit long-range magnetic order in the bulk are still very hard to synthesize. Chromium and manganese are the cutoff elements when transitioning through the 3dmetals that still form stable full and doped MAX phases, respectively. An iron-based (on the M-site) bulk MAX phase does not exist. Therefore, other strategies to induce long-range magnetic ordering in bulk MAX phases are necessary to open the path to new functional materials. Here, we demonstrate the nonconventional synthesis of a hitherto unknown MAX phase solid-solution (V1–xCrx)2GaC by microwave heating. The full series with 0 < x < 1 (x = 0.20, 0.40, 0.50, 0.60, 0.80) forms almost single phase with minimal differences in their morphology. Their magnetic properties, however, differ rather significantly, with a maximum susceptibility around x = 0.80. Both the experimental and theoretical/ab initio magnetic analysis confirm that the solid-solution (V1–xCrx)2GaC is an itinerant Pauli paramagnet that almost fulfills the Stoner criterion for ferromagnetic order (for compositions with x around 0.80). This is a powerful insight into how chemical composition couples with electronic structure and the resulting bulk magnetic properties because it provides crucial guidelines to produce long-range ordered magnetic MAX phases.

Ternary orthorhombic Laves phases Sr2Pd3Sn, Eu2Pd3Sn and Eu2Pd3In

Abstract The ternary Laves phases Sr2Pd3Sn, Eu2Pd3Sn and Eu2Pd3In were synthesized by induction melting of the elements in sealed tantalum ampoules. The polycrystalline products were characterized through their powder X-ray diffraction patterns. The structure of Eu2Pd3Sn was refined from single crystal X-ray diffractometer data: Mg2MnGa3 type, Cmcm, a = 583.36(5), b = 908.31(7), c = 958.06(8) pm, wR2 = 0.0366, 557 F 2 values, 23 variables. The palladium and tin atoms show the inverse coloring on the network of condensed tetrahedra of Mg2MnGa3, i.e., MnGa3 versus Pd3Sn. Refinement of the occupancy parameters revealed small defects for the europium site, leading to composition Eu1.962(6)Pd3Sn for the studied crystal. Sr2Pd3Sn is a Pauli paramagnet and Eu2Pd3Sn shows Curie-Weiss paramagnetism (7.86(1) µB Eu atom−1 and Θ P = 48.1(1) K). Ferromagnetic ordering is observed below T C = 46.1(1) K. The 119Sn and 151Eu Mössbauer spectra of Sr2Pd3Sn and Eu2Pd3Sn are discussed with respect to electron density changes as a function of the tin content and the ionicity in the sequence of the stannides Sr2Pd3Sn/Eu2Pd3Sn → Sr2Pd2Sn/Eu2Pd2Sn → EuPdSn → EuPdSn2.

Mössbauer-spectroscopic characterization of the stannides Sr2Pd2Sn and Eu2Pd2Sn

Abstract The Ca2Pd2Ge-type stannides Sr2Pd2Sn and Eu2Pd2Sn were synthesized by reaction of the elements in sealed tantalum ampoules in a high-frequency furnace and characterized by powder X-ray diffraction. The structure of Sr2Pd2Sn (Fdd2, a = 1063.95(5), b = 1623.22(9), c = 594.63(14) pm, wR2 = 0.0472, 972 F 2 values and 26 variables) was refined from single-crystal X-ray diffractometer data. The striking structural motif features equidistant chains formed by the palladium atoms (304.7 pm Pd–Pd), which are interlinked by the tin atoms (266.9 and 268.7 pm Pd–Sn). Together, the palladium and tin atoms form a three-dimensional [Pd2Sn] δ– polyanionic network in which the strontium atoms reside in larger cavities. The divalent character of europium in Eu2Pd2Sn was manifested by 151Eu Mössbauer spectroscopy. The isomer shift is δ = −9.48(1) mm s−1 at room temperature. The results of 119Sn Mössbauer-spectroscopic experiments have confirmed the tin site determined by the single-crystal study, the isomer shifts being δ = 1.71(1) mm s−1 for Eu2Pd2Sn and δ = 1.73(1) mm s−1 for Sr2Pd2Sn. Sr2Pd2Sn is a Pauli paramagnet with a susceptibility of 2.2(1) × 10−5 emu mol−1 at room temperature. Eu2Pd2Sn shows Curie-Weiss paramagnetism with an experimental magnetic moment of 7.85(1) µB per Eu atom, confirming divalent europium. The europium magnetic moments order antiferromagnetically at T N = 14 K.

Artificial magnetism for a harmonically trapped Fermi gas in a synthetic magnetic field

We have analytically explored the artificial magnetism for a 3D spin-polarized harmonically trapped ideal Fermi gas of electrically neutral particles exposed to a uniform synthetic magnetic field. Though polarization of the spin is necessary for trapping electrically neutral atoms in a magneto-optical trap, Pauli paramagnetism can not be studied for the spin-polarized Fermi system. However, it is possible to study Landau diamagnetism and de Haas-van Alphen effect for such a system. We have unified the artificial Landau diamagnetism and the artificial de Haas-van Alphen effect in a single framework for all temperatures as well as for all possible magnitudes of the synthetic magnetic field in the thermodynamic limit. Our prediction is testable in the present-day experimental setup for ultracold fermionic atoms in magneto-optical trap.

The palladium-rich silicides RE 3Pd20Si6 (RE = Sc, Y and Lu)

Abstract The silicides RE 3Pd20Si6 (RE = Sc, Y and Lu) were synthesized from the elements by arc-melting. The structures of Y3Pd20Si6 and Lu3Pd20Si6 were refined from single crystal X-ray diffractometer data: Mg3Ni20B6 type, F m 3 ‾ m $Fm\overline{3}m$ , a = 1216.04(8) pm, wR = 0.0328, 219 F 2 values, 14 variables for Y3Pd20Si6 and a = 1211.69(10) pm, wR = 0.0374, 217 F 2 values, 14 variables for Lu3Pd20Si6. The isotypy of Sc3Pd20Si6 was confirmed on the basis of a Guinier powder pattern (a = 1202.8(3) pm). The RE 3Pd20Si6 structures contain two crystallographically independent RE sites with relatively large coordination numbers, i.e. RE1@Pd16 and RE2@Pd12Si6. These polyhedra are arranged in a CaF2 related pattern with RE2@Pd12Si6 forming the fcc substructure and the RE1@Pd16 polyhedra filling the tetrahedral voids. The silicon atoms have slightly distorted square antiprismatic palladium coordination (4 × 239 pm Si–Pd1 and 4 × 245 pm Si–Pd2). Temperature dependent magnetic susceptibility measurements of the Lu3Pd20Si6 sample indicate Pauli paramagnetism.

Density polarization effect of spin-up and spin-down electrons on magnetosonic solitons in a dense plasma with oblique magnetic field

Nonlinear wave propagation of fast and slow magnetosonic waves is investigated in a magnetized quantum plasma with spin polarization effects of degenerate electrons. The multi-fluid quantum magnetohydrodynamic model is considered and two separate fluid dynamic equations for degenerate electrons i.e. spin-up and spin-down states (Pauli paramagnetism) with their different Fermi pressures. The ions are assumed to be classical and external magnetic field lies in a plane. The magnetization energy and current density of electrons due to the spin-1/2 effects are included in the momentum equation of the degenerate electrons and Maxwell equations, respectively. A Korteweg-de-Vries (KdV) equation is derived for nonlinear magnetosonic waves in a dense magnetized plasma with the inclusion of electron spin effects and oblique external magnetic field. The electron inertial effect (which causes wave dispersion) of both spin-up and spin-down state electrons is also included in the model. It is found that electron spin polarization density has significant effects on the phase speed and soliton structures (i.e. its width and amplitude) of fast (hump) and slow (dip) magnetosonic waves in a dense magnetized plasma. The present theoretical study along with the obtained numerical results may have possible applications towards many realistic astrophysical scenarios.

Entangled origins of the nonmagnetic states of U and Fe atoms in hydrogenated UFeGe

The experimental ground state of hydrogenated UFeGe (H-UFeGe) is nonmagnetic (NM). This result is not expected since, first, both U and Fe atoms tend to be magnetic in their compounds and, second, the hydrogenation is considered as favorable for magnetism. There are two main scenarios to explain the observation of nonmagnetic U atoms in the U based materials: Pauli paramagnetism of the Stoner type and Kondo-type screening of the atomic 5f moments. We apply the local density approximation (LDA) and $\mathrm{LDA}+U$ methods to investigate the origin of the ground state of H-UFeGe. The LDA calculations give in agreement with experiment the NM state as the only self-consistent state. The absence of the magnetic moments of both U and Fe atoms is the result of the U 5f-Fe 3d hybridization. The $\mathrm{LDA}+U$ calculations with different $U$ values reveal sensitive competition between NM and magnetic phases. The result of this competition depends nonmonotonously on the value of parameter $U$. We explain this nonmonotonous behavior by multiorbital nature of the 5f electron contributions to the electron structure of H-UFeGe combined with different responses of different orbitals to the correlation governed by $U$. Employing constraint calculations we demonstrate that in the magnetic phases the Fe atomic moments can be treated as induced by the U moments. Since the directions of the U and Fe spin moments are opposite, the mechanism of the induction is nontrivial. It includes the spin-projection-dependent charge redistribution and a peculiar influence of the spin polarization on the interatomic hybridization. We compare H-UFeGe with two other materials containing U and Fe atoms and establish important differences.