Probing Magnetism in the Vortex Phase of PuCoGa_{5} by X-Ray Magnetic Circular Dichroism.

We measure x-ray magnetic circular dichroism (XMCD) spectra at the Pu M_{4,5} absorption edges from a newly prepared high-quality single crystal of the heavy-fermion superconductor ^{242}PuCoGa_{5}, exhibiting a critical temperature T_{c}=18.7 K. The experiment probes the vortex phase below T_{c} and shows that an external magnetic field induces a Pu 5f magnetic moment at 2 K equal to the temperature-independent moment measured in the normal phase up to 300 K by a superconducting quantum interference device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa_{5} have a nonmagnetic singlet ground state resulting from the hybridization of the conduction electrons with the intermediate-valence 5f electronic shell. Unexpectedly, XMCD spectra show that the orbital component of the 5f magnetic moment increases significantly between 30 and 2 K; the antiparallel spin component increases as well, leaving the total moment practically constant. We suggest that this indicates a low-temperature breakdown of the complete Kondo-like screening of the local 5f moment.

Magnetic polarization of the americium J=0 ground state in AmFe(2).

Trivalent americium has a nonmagnetic (J=0) ground state arising from the cancellation of the orbital and spin moments. However, magnetism can be induced by a large molecular field if Am^{3+} is embedded in a ferromagnetic matrix. Using the technique of x-ray magnetic circular dichroism, we show that this is the case in AmFe_{2}. Since ⟨J_{z}⟩=0, the spin component is exactly twice as large as the orbital one, the total Am moment is opposite to that of Fe, and the magnetic dipole operator ⟨T_{z}⟩ can be determined directly; we discuss the progression of the latter across the actinide series.

Low temperature heat capacity and magnetic properties of UF3.

The low temperature heat capacity of UF(3) has been measured using an adiabatic low temperature calorimeter in the temperature range from 10 to 350 K. These data are complemented at the lowest temperature region with data obtained with a Quantum Design PPMS-14 device in the temperature range from 0.5 to 20 K. Good agreement between both techniques has been found, and from these experimental results the absolute entropy of UF(3) at 298.15 K has been determined as 126.8 ± 2.5 J K(-1) mol(-1). On the basis of the specific heat data and the magnetization measurements performed on a SQUID device, a transition at 1.59 K attributed to Curie temperature of a ferromagnetic transition has been found in this study. This observation makes UF(3) a unique compound with an unusually low ferromagnetic ordering temperature.

Superexchange coupling and slow magnetic relaxation in a transuranium polymetallic complex.

{Np(VI)O2Cl2}{Np(V)O2Cl(thf)3}2 is the first studied example of a polymetallic transuranic complex displaying both slow relaxation of the magnetization and effective superexchange interactions between 5f centers. The coupling constant for Np(V)-Np(VI) pairs is 10.8 K, more than 1 order of magnitude larger than the common values found for rare-earth ions in similar environments. The dynamic magnetic behavior displays slow relaxation of magnetization of molecular origin with an energy barrier of 140 K, which is nearly twice the size of the highest barrier found in polymetallic clusters of the d block. Our observations also suggest that future actinide-based molecular magnets will have very different behavior to lanthanide-based clusters.

Electronic properties of Pu19Os simulating ß-Pu: the strongly correlated Pu phase.

We established the basic electronic properties of ζ-Pu19Os, which is a close analogue to ß-Pu, and its low-temperature variety, η-Pu19Os. Their magnetic susceptibility is 15% higher than for δ-Pu. A specific heat study of ζ-Pu19Os shows a soft lattice similar to δ-Pu, leading to a low Debye temperature Θ D = 101 K. The linear electronic coefficient γ related to the quasiparticle density of states at the Fermi level points to a higher value, 55 ± 2 mJ (mol Pu K2)-1, compared to 40 mJ (mol K2)-1 for δ-Pu. The results confirm that ß-Pu is probably the most strongly correlated Pu phase, as had been indicated by resistivity measurements. The volume and related Pu-Pu spacing is clearly not the primary tuning parameter for Pu metal, as the ß-Pu density stands close to the ground-state α-phase and is much higher than that for δ-Pu. The η-Pu19Os phase has a record γ-value of 74 ± 2 mJ (mol Pu K2)-1. The enhancement is not reproduced by LDA+DMFT calculations in the fcc structure, which suggests that multiple diverse sites can be the key to the understanding of ß-Pu.

Magnetic properties of NpNiGa(5).

We have investigated a polycrystalline sample of NpNiGa(5) by magnetization, specific heat and (237)Np Mössbauer spectroscopy. We confirm that a ferromagnetic order sets in at T(C)≈30 K and that NpNiGa(5) undergoes a second transition at T(N)≈18 K. Mössbauer data indicate that the transition at T(N) is accompanied by a steep increase of the Np magnetic moment, which saturates to a value of 0.94 µ(B), in good agreement with the recently published neutron diffraction results. The Sommerfeld specific heat coefficient γ = 114 mJ mol(-1) K(-2) is the highest among the NpTGa(5) compounds. It compares to the ones observed in the PuTGa(5) superconductors. The trend of the isomer shift along the NpTGa(5) (T = Fe, Co, Ni, Rh) series points to a tendency towards localization of the 5f electrons when increasing the number of d electrons of the transition metal T. Neither fully localized nor fully itinerant models are able to reproduce the whole experimental data. Realistic models should include the dual nature of the 5f electrons, i.e. consider the difference in the degree of itinerancy among 5f electrons in the NpTGa(5) compounds.

The linear and non-linear magnetic response of a tri-uranium single molecule magnet.

We report here low temperature magnetization isotherms for the single molecule magnet, (UO2-L)3. By analyzing the low temperature magnetization in terms of M = χ 1 B + χ 3 B 3 we extract the linear susceptibility χ 1 and the leading order nonlinear susceptibility χ 3. We find that χ 1 exhibits a peak at a temperature of T 1 = 10.4 K with χ 3 also exhibiting a peak but at a reduced temperature T 3 = 5 K. At the lowest temperatures the isotherms exhibit a critical field B c = 11.5 T marked by a clear point of inflection. A minimal Hamiltonian employing S = 1 (pseudo) spins with only a single energy scale (successfully used to model the behavior of bulk f-electron metamagnets) is shown to provide a good description of the observed linear scaling between T 1, T 3 and B c. We further show that a Heisenberg Hamiltonian previously employed by Carretta et al (2013 J. Phys.: Condens. Matter 25 486001) to model this single molecule magnet gives formulas for the angle averaged susceptibilities (in the Ising limit) very similar to those of the minimal model.

Synthesis and investigation of neptunium zirconium phosphate, a member of the NZP family: crystal structure, thermal behaviour and Mössbauer spectroscopy studies.

A new double neptunium zirconium phosphate of the type MxZr2(PO4)3 (M = Np), crystallizing in the structure type NaZr2(PO4)3 (NZP, NASICON), was synthesized by solid state reactions at high temperatures and characterized by X-ray diffraction, infrared spectroscopy and Mössbauer spectroscopy. The Rietveld refinement of the XRD pattern together with the analysis of the IR spectra of the sample confirmed the space group P3[combining macron]c, the same as that for the lanthanide analogues Ln0.33Zr2(PO4)3. However, Mössbauer studies revealed the presence of neptunium in the two oxidation states +3 and +4, indicating a two-phase NZP system with different crystallographic environments of the neptunium atoms. The thermal behaviour of the sample was followed up to 1400 °C by thermogravimetric analysis.

Structural investigation of Na3NpO4 and Na3PuO4 using X-ray diffraction and (237)Np Mössbauer spectroscopy.

α-Na3NpO4 and α-Na3PuO4 exhibit an orthorhombic structure (Z = 8), in space group Fmmm, with lattice parameters a = 13.352(2) Å, b = 9.629(2) Å, and c = 6.673(2) Å for the neptunium compound, and a = 13.302(2) Å, b = 9.634(2) Å, and c = 6.651(2) Å for the plutonium analogue. The corresponding structure has been solved ab initio as no structural analogue could be found in the literature. The pentavalent state of neptunium has moreover been confirmed by (237)Np Mössbauer spectroscopy, and the local structural properties inferred from the X-ray Rietveld refinement have been related to the fitted quadrupole coupling constant and asymmetry parameters. The existence of a low temperature metastable m phase of Na3NpO4 and Na3PuO4, of the NaCl type, has also been suggested.

Absence of superconductivity in fluorine-doped neptunium pnictide NpFeAsO.

X-ray diffraction, specific heat, magnetic susceptibility and inelastic x-ray scattering measurements on the transurarium oxypnictides NpFeAsO and NpFeAsO0.85F0.15 are presented. No superconductivity down to 2 K was observed upon fluorine doping, contrary to the structurally analogous rare-earth pnictides. No modification of the phonon density of states was observed upon doping with fluorine. We discuss our results in light of the latest experimental and theoretical studies on the role of phonons in the superconducting pnictide compounds.

A plutonium-based single-molecule magnet.

The magnetic properties of the 5f(5) [tris-(tri-1-pyrazolylborato)-plutonium(III)] complex have been investigated by ac susceptibility measurements, showing it to be the first plutonium single-molecule magnet; its magnetic relaxation slows down with decreasing temperature through a thermally activated mechanism followed by a quantum tunnelling regime below 5 K.

(237)Np Mössbauer effect study on NpFeAsO.

We report (237)Np Mössbauer measurements on NpFeAsO. The Np atoms were found to occupy only one crystallographic site. The value of the isomer shift (δ âˆ¼ 9.1 mm s(-1) versus NpAl2) indicates a 5f(4) electronic configuration (Np(3+) ions). The magnetic ordering of the Np sublattice below 60 K is established and the saturated ordered magnetic moment is determined to be 1.73µB at 3.6 K. The unique set of hyperfine parameters exclude a modulated magnetic structure or spin waves on the Np site. The neptunium magnetic moments µNp are found to lie along the tetragonal c-axis.

Magnetic properties and chiral states of a trimetallic uranium complex.

The magnetic properties of the triangular molecular nanomagnet [UO2L]3 (L = 2-(4-tolyl)-1,3-bis(quinolyl)malondiiminate) have been investigated through electron paramagnetic resonance spectroscopy, high-field magnetization and susceptibility measurements. The experimental findings are well reproduced by a microscopic model including exchange interactions and local crystal fields. These results show that [UO2L]3 is characterized by a non-magnetic ground doublet corresponding to two oppositely twisted chiral arrangements of the uranium moments. The non-axial character of single-ion crystal fields leads to quantum tunneling of the noncollinear magnetization in the presence of a magnetic field applied perpendicularly to the triangle plane.

Strong-coupling d-wave superconductivity in PuCoGa5 probed by point-contact spectroscopy.

Superconductivity is due to an attractive interaction between electrons that, below a critical temperature, drives them to form Cooper pairs and to condense into a ground state separated by an energy gap from the unpaired states. In the simplest cases, the pairing is mediated by lattice vibrations and the wavefunction of the pairs is isotropic. Less conventional pairing mechanisms can favour more exotic symmetries of the Cooper pairs. Here, we report on point-contact spectroscopy measurements in PuCoGa(5), a moderate heavy-fermion superconductor with a record high critical temperature T(c)=18.5 K. The results prove that the wavefunction of the paired electrons has a d-wave symmetry, with four lobes and nodes, and show that the pairing is likely to be mediated by spin fluctuations. Electronic structure calculations, which take into account the full structure of the f-orbital multiplets of Pu, provide a hint of the possible origin of these fluctuations.

Localized 5f electrons in superconducting PuCoIn5: consequences for superconductivity in PuCoGa5.

The physical properties of the first In analog of the PuMGa(5) (M = Co, Rh) family of superconductors, PuCoIn(5), are reported. With its unit cell volume being 28% larger than that of PuCoGa(5), the characteristic spin-fluctuation energy scale of PuCoIn(5) is three to four times smaller than that of PuCoGa(5), which suggests that the Pu 5f electrons are in a more localized state relative to PuCoGa(5). This raises the possibility that the high superconducting transition temperature T(c) = 18.5 K of PuCoGa(5) stems from the proximity to a valence instability, while the superconductivity at T(c) = 2.5 K of PuCoIn(5) is mediated by antiferromagnetic spin fluctuations associated with a quantum critical point.

Magnetic and electronic properties of NpFeGa5.

NpFeGa(5) single crystals prepared by the Ga-flux method have been investigated by magnetisation, specific heat and (237)Np Mössbauer spectroscopy measurements. An antiferromagnetic (AF) transition has been observed at T(N) ~114 K. The second AF transition which takes place at T* ~74 K has only been detected in the magnetisation data. A saturated ordered Np moment of 1.00(5) µ(B) and the occurrence of an Np(3 + ) charge state were inferred from the Mössbauer data. The angle between the Np ordered moment and the basal plane was shown to be ~17°, in good agreement with the value observed by neutron diffraction in the low temperature AF phase. The absence of change of the quadrupole interaction parameters at T* did not allow us to gain information on the Np moment reorientation at T*. The trend of the isomer shift along the NpTGa(5) series and the discrepancy between the Np moments determined by neutron diffraction and Mössbauer spectroscopy indicated a partial spatial delocalisation of the 5f electrons in NpFeGa(5).

Electronic state of PuCoGa5 and NpCoGa5 as probed by polarized neutrons.

By using single crystals and polarized neutrons, we have measured the orbital and spin components of the microscopic magnetization in the paramagnetic state of NpCoGa(5) and PuCoGa(5). The microscopic magnetization of NpCoGa(5) agrees with that observed in bulk susceptibility measurements and the magnetic moment has spin and orbital contributions as expected for intermediate coupling. In contrast, for PuCoGa(5), which is a superconductor with a high transition temperature, the microscopic magnetization in the paramagnetic state is small, temperature-independent, and significantly below the value found with bulk techniques at low temperatures. The orbital moment dominates the magnetization.

Specific heat of delta-Pu stabilized by Am.

Detailed specific heat C(p) measurements of delta-Pu stabilized by Am (8%-20%) were performed in the temperature range 4.5-300 K. The coefficient of the electronic specific heat gamma, which reflects the quasiparticle density of states at the Fermi level E(F), is smaller than originally assumed and, depending on the estimate of phonon contributions, a value between 35 and 55 mJ/mol K2 can be deduced for Pu-8% Am. For higher Am concentrations, which expand the lattice, gamma decreases slightly with the Am content. An applied magnetic field of 9 T had no effect on C(p). The results strongly suggest that itinerant 5f states at E(F) are not appropriate for describing delta-Pu.

Determination of the antiferroquadrupolar order parameters in UPd(3).

By combining accurate heat capacity and x-ray resonant scattering results we have resolved the long standing question regarding the nature of the quadrupolar ordered phases in UPd(3). The order parameter of the highest temperature quadrupolar phase has been uniquely determined to be antiphase Q{zx} in contrast to the previous conjecture of Q{x{2}-y{2}}. The azimuthal dependence of the x-ray scattering intensity from the quadrupolar superlattice reflections indicates that the lower temperature phases are described by a superposition of order parameters. The heat capacity features associated with each of the phase transitions characterize their order, which imposes restrictions on the matrix elements of the quadrupolar operators.

Plutonium-based superconductivity with a transition temperature above 18 K.

Plutonium is a metal of both technological relevance and fundamental scientific interest. Nevertheless, the electronic structure of plutonium, which directly influences its metallurgical properties, is poorly understood. For example, plutonium's 5f electrons are poised on the border between localized and itinerant, and their theoretical treatment pushes the limits of current electronic structure calculations. Here we extend the range of complexity exhibited by plutonium with the discovery of superconductivity in PuCoGa5. We argue that the observed superconductivity results directly from plutonium's anomalous electronic properties and as such serves as a bridge between two classes of spin-fluctuation-mediated superconductors: the known heavy-fermion superconductors and the high-T(c) copper oxides. We suggest that the mechanism of superconductivity is unconventional; seen in that context, the fact that the transition temperature, T(c) approximately 18.5 K, is an order of magnitude greater than the maximum seen in the U- and Ce-based heavy-fermion systems may be natural. The large critical current displayed by PuCoGa5, which comes from radiation-induced self damage that creates pinning centres, would be of technological importance for applied superconductivity if the hazardous material plutonium were not a constituent.