Structural, electronic, and magnetic characteristics of Np_2Co_(17)

A previously unknown neptunium-transition-metal binary compound Np_2Co_(17) has been synthesized and characterized by means of powder x-ray diffraction, ^(237)Np Mössbauer spectroscopy, superconducting-quantum-interference-device magnetometry, and x-ray magnetic circular dichroism (XMCD). The compound crystallizes in a Th_2Ni_(17)-type hexagonal structure with room-temperature lattice parameters α=8.3107(1) Å and c=8.1058(1) Å. Magnetization curves indicate the occurrence of ferromagnetic order below T_C>350 K. Mössbauer spectra suggest a Np^(3+) oxidation state and give an ordered moment of μ_(Np)=1.57(4) μ_B and μ_(Np)=1.63(4) μ_B for the Np atoms located, respectively, at the 2b and 2d crystallographic positions of the P6_3/mmc space group. Combining these values with a sum-rule analysis of the XMCD spectra measured at the neptunium M_(4,5) absorption edges, one obtains the spin and orbital contributions to the site-averaged Np moment [μ_S=−1.88(9) μ_B, μ_L=3.48(9) μ_B]. The ratio between the expectation value of the magnetic-dipole moment and the spin magnetic moment (m_(md)/μS=+1.36) is positive as predicted for localized 5f electrons and lies between the values calculated in intermediate-coupling (IC) and jj approximations. The expectation value of the angular part of the spin-orbit-interaction operator is in excellent agreement with the IC estimate. The ordered moment averaged over the four inequivalent Co sites, as obtained from the saturation value of the magnetization, is μ_(Co)≃1.6 μ_B. The experimental results are discussed against the predictions of first-principles electronic-structure calculations based on the spin-polarized local-spin-density approximation plus the Hubbard interaction

Probing magnetism in the vortex phase of PuCoGa5 by X-ray magnetic circular dichroism

We have measured X-ray magnetic circular dichroism (XMCD) spectra at the Pu M4;5 absorption edges from a newly-prepared high-quality single crystal of the heavy fermion superconductor 242PuCoGa5, exhibiting a critical temperature Tc = 18.7 K. The experiment probes the vortex phase below Tc 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 SQUID device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa5 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.JRC.G.I.5-Advanced Nuclear Knowledg

Magnetic state of plutonium ion in metallic Pu and its compounds

By LDA+U method with spin-orbit coupling (LDA+U+SO) the magnetic state and electronic structure have been investigated for plutonium in \delta and \alpha phases and for Pu compounds: PuN, PuCoGa5, PuRh2, PuSi2, PuTe, and PuSb. For metallic plutonium in both phases in agreement with experiment a nonmagnetic ground state was found with Pu ions in f^6 configuration with zero values of spin, orbital, and total moments. This result is determined by a strong spin-orbit coupling in 5f shell that gives in LDA calculation a pronounced splitting of 5f states on f^{5/2} and f^{7/2} subbands. A Fermi level is in a pseudogap between them, so that f^{5/2} subshell is already nearly completely filled with six electrons before Coulomb correlation effects were taken into account. The competition between spin-orbit coupling and exchange (Hund) interaction (favoring magnetic ground state) in 5f shell is so delicately balanced, that a small increase (less than 15%) of exchange interaction parameter value from J_H=0.48eV obtained in constrain LDA calculation would result in a magnetic ground state with nonzero spin and orbital moment values. For Pu compounds investigated in the present work, predominantly f^6 configuration with nonzero magnetic moments was found in PuCoGa5, PuSi2, and PuTe, while PuN, PuRh2, and PuSb have f^5 configuration with sizeable magnetic moment values. Whereas pure jj coupling scheme was found to be valid for metallic plutonium, intermediate coupling scheme is needed to describe 5f shell in Pu compounds. The results of our calculations show that both spin-orbit coupling and exchange interaction terms in the Hamiltonian must be treated in a general matrix form for Pu and its compounds.Comment: 20 pages, LaTeX; changed discussion on reference pape