Atomic-volume variations of (alpha)-Pu alloyed with Al, Ga, and Am from first-principles theory

First-principles methods are employed to calculate the ground-state atomic densities (or volumes) of {alpha}-Pu alloyed with Al, Ga, and Am. Three configurations for the alloying atom are considered. (1) It is located at the most open and energetically most favorably site. (2) It is located in the least open site. (3) It is randomly distributed within the {alpha}-Pu matrix. When alloyed with Al or Ga, {alpha}-Pu behaves similarly, it expands considerably for configurations (2) and (3), while for (1) only small changes of the density occurs. Interestingly, for Am the alloying effects are quite different from that of Al and Ga. Small expansion is noted for the ordered configurations (1) and (2), whereas for the disordered (3), only insignificant changes of the density take place. The bonding character is thus differently influenced in Pu by the addition of Al and Ga on one hand and Am on the other. This is consistent with the view that Al and Ga stabilize the {delta} over the {alpha} phase in Pu by a different mechanism than Am, as has been discussed in recent publications

Spin-orbit holds the heavyweight title for Pu and Am: Exchange regains it for Cm

The conclusions of this paper are: (1) The 5f electrons in Cm are near an LS coupling scheme. (2) This coupling scheme allows for a large spin polarization of the 5f electrons, which in turn stabilizes the Cm III crystal structure. (3) Results for Cm show us the recipe for magnetic stabilization of the crystal structure of metals: (A) The metal must be near the itinerant-localized transition where multiple crystal structures have close energies; (B) The metal is just on the magnetic side of the transition; and (C) There must be a magnetic moment large enough to overcome the energy difference between crystal structures, thus dictating the atomic geometry. (4) These results solidify our understanding of magnetically-stabilized metals, showing us where to look for engineered materials with magnetic applications

Emergence of Strong Exchange Interaction in the Actinide Series: The Driving Force for Magnetic Stabilization of Curium

Using electron energy-loss spectroscopy in a transmission electron microscope, many-electron atomic spectral calculations and density functional theory, we examine the electronic and magnetic structure of Cm metal. We show that angular momentum coupling in the 5f states plays a decisive role in the formation of the magnetic moment. The 5f states of Cm in intermediate coupling are strongly shifted towards the LS coupling limit due to exchange interaction, unlike most actinide elements where the effective spin-orbit interaction prevails. It is this LS-inclined intermediate coupling that is the key to producing the large spin polarization which in turn dictates the newly found crystal structure of Cm under pressure

The stabilizing role of itinerant ferromagnetism in inter-granular cohesion in iron

We present a simple, general energy functional for ferromagnetic materials based upon a local spin density extension to the Stoner theory of itinerant ferromagnetism. The functional reproduces well available ab initio results and experimental interfacial energies for grain boundaries in iron. The model shows that inter-granular cohesion along symmetric tilt boundaries in iron is dependent upon strong magnetic structure at the interface, illuminates the mechanisms underlying this structure, and provides a simple explanation for relaxation of the atomic structure at these boundaries.Comment: In review at Phys. Rev. Lett. Submitted 23 September 1997; revised 16 March 199

Modelling charge self-trapping in wide-gap dielectrics: Localization problem in local density functionals

We discuss the adiabatic self-trapping of small polarons within the density functional theory (DFT). In particular, we carried out plane-wave pseudo-potential calculations of the triplet exciton in NaCl and found no energy minimum corresponding to the self-trapped exciton (STE) contrary to the experimental evidence and previous calculations. To explore the origin of this problem we modelled the self-trapped hole in NaCl using hybrid density functionals and an embedded cluster method. Calculations show that the stability of the self-trapped state of the hole drastically depends on the amount of the exact exchange in the density functional: at less than 30% of the Hartree-Fock exchange, only delocalized hole is stable, at 50% - both delocalized and self-trapped states are stable, while further increase of exact exchange results in only the self-trapped state being stable. We argue that the main contributions to the self-trapping energy such as the kinetic energy of the localizing charge, the chemical bond formation of the di-halogen quasi molecule, and the lattice polarization, are represented incorrectly within the Kohn-Sham (KS) based approaches.Comment: 6 figures, 1 tabl

Capabilities for Testing the Electronic Configuration in Pu

The benchmarking of theoretical modeling is crucial to the ultimate determination of the nature of the electronic structure of Pu. Examples of experimental techniques used for cross checking state of the art calculations will be given

On The Electronic Configuration in Pu

X-Ray Absorption Spectroscopy (XAS) and Photoelectron Spectroscopy (PES) have been performed upon highly radioactive samples, particularly Plutonium, at the Advanced Light Source in Berkeley, CA, USA. First results from alpha and delta Plutonium are reported as well as a detailed analysis of sample quality

On the electronic configuration in Pu: spectroscopy and theory

Photoelectron spectroscopy, synchrotron-radiation-based x-ray absorption, electron energy-loss spectroscopy, and density-functional calculations within the mixed-level and magnetic models, together with canonical band theory have been used to study the electron configuration in Pu. These methods suggest a 5f{sup n} configuration for Pu of 5 {le} n < 6, with n {ne} 6, contrary to what has recently been suggested in several publications. We show that the n = 6 picture is inconsistent with the usual interpretation of photoemission and x-ray absorption spectra. Instead, these spectra support the traditional conjecture of a 5f{sup 5} configuration in Pu as is obtained by density-functional theory. We further argue, based on 5f-band filling, that an n = 6 hypothesis is incompatible with the position of Pu in the actinide series and its monoclinic ground-state phase