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Intrinsic properties of a compound (e.g. electronic structure, crystallographic structure, optical and magnetic properties) define notably its chemical and physical behavior. In the case of nanomaterials, these fundamental properties depend on the occurrence of quantum mechanical size effects and on the considerable increase of the surface to bulk ratio. However, the literature on this size-dependence and on the involved mechanisms is quite elusive and scarce. Here, we explore the size-dependence of both crystal and electronic properties of CeO2 nanoparticles (NPs) with different sizes by state-of-the art spectroscopic techniques. XRD, XPS and HERFD-XANES demonstrate that the as-synthesized NPs crystallize in the fluorite structure and they are predominantly composed of Ce IV ions. The strong dependence of the lattice parameter with the NPs size was attributed to the presence of adsorbed species at the NPs surface thanks to FTIR and TGA measurements. In addition, the size-dependence of the t2g level in the Ce LIII XANES spectra was experimentally observed by HERFD-XANES and confirmed by theoretical calculations.

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.

A neptunium analog of the LaFeAsO tetragonal layered compound has been synthesized and characterized by a variety of experimental techniques. The occurrence of long-range magnetic order below a critical temperature T N = 57 K is suggested by anomalies in the temperature-dependent magnetic susceptibility, electrical resistivity, Hall coefficient, and specific-heat curves. Below T N , powder neutron diffraction measurements reveal an antiferromagnetic structure of the Np sublattice, with an ordered magnetic moment of 1.70 ± 0.07μ B aligned along the crystallographic c axis. No magnetic order has been observed on the Fe sublattice, setting an upper limit of about 0.3μ B for the ordered magnetic moment on the iron. High-resolution x-ray powder diffraction measurements exclude the occurrence of lattice transformations down to 5 K, in sharp contrast to the observation of a tetragonal-to-orthorhombic distortion in the rare-earth analogs, which has been associated with the stabilization of a spin-density wave on the iron sublattice. Instead, a significant expansion of the NpFeAsO lattice parameters is observed with decreasing temperature below T N , corresponding to a relative volume change of about 0.2% and to an Invar behavior between 5 and 20 K. First-principles electronic structure calculations based on the local spin density plus Coulomb interaction and the local density plus Hubbard-I approximations provide results in good agreement with the experimental findings.

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 PuCoGa5, a moderate heavy-fermion superconductor with a record high critical temperature Tc=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.