Structural and Magnetic Properties of Trigonal Iron

First principles calculations of the electronic structure of trigonal iron were performed using density function theory. The results are used to predict lattice spacings, magnetic moments and elastic properties; these are in good agreement with experiment for both the bcc and fcc structures. We find however, that in extracting these quantities great care must be taken in interpreting numerical fits to the calculated total energies. In addition, the results for bulk iron give insight into the properties of thin iron films. Thin films grown on substrates with mismatched lattice constants often have non-cubic symmetry. If they are thicker than a few monolayers their electronic structure is similar to a bulk material with an appropriately distorted geometry, as in our trigonal calculations. We recast our bulk results in terms of an iron film grown on the (111) surface of an fcc substrate, and find the predicted strain energies and moments accurately reflect the trends for iron growth on a variety of substrates.Comment: 11 pages, RevTeX,4 tar'd,compressed, uuencoded Postscript figure

Cancellation of spin and orbital magnetic moments in (delta)-Pu: theory

Density functional theory (DFT), in conjunction with the fixed-spin-moment (FSM) method, spin-orbit coupling (SO), and orbital polarization (OP), is shown to retain key features of the conventional DFT treatment of {delta}-Pu while at the same time not producing the substantial net magnetic moments commonly predicted by this theory. It is shown that when a small adjustment of the spin moment (less than 20%) is allowed, a complete spin- and orbital-moment cancellation occurs which results in a zero net magnetic moment in {delta}-Pu. This minor modification, accomplished by the FSM method, is shown to have a very small effect on the calculated total energy as well as the electron density-of-states (DOS). The photoemission spectra (PES), obtained from the DOS of the present model, compares equal or better to measured spectra, than that of two other recent non-magnetic models for {delta}-Pu

Phase stability in heavy f-electron metals from first-principles theory

The structural phase stability of heavy f-electron metals is studied by means of density-functional theory (DFT). These include temperature-induced transitions in plutonium metal as well as pressure-induced transitions in the trans-plutonium metals Am, Cm, Bk, and Cf. The early actinides (Th-Np) display phases that could be rather well understood from the competition of a crystal-symmetry breaking mechanism (Peierls distortion) of the 5f states and electrostatic forces, while for the trans-plutonium metals (Am-Cf) the ground-state structures are governed by 6d bonding. We show in this paper that new physics is needed to understand the phases of the actinides in the volume range of about 15-30 {angstrom}{sup 3}. At these volumes one would expect, from theoretical arguments made in the past, to encounter highly complex crystal phases due to a Peierls distortion. Here we argue that the symmetry reduction associated with spin polarization can make higher symmetry phases competitive. Taking this into account, DFT is shown to describe the well-known phase diagram of plutonium and also the recently discovered complex and intriguing high-pressure phase diagrams of Am and Cm. The theory is further applied to investigate the behaviors of Bk and Cf under compression

Delocalization and new phase in Americium: theory

Density-functional electronic structure calculations have been used to investigate the high pressure behavior of Am. At about 80 kbar (8 GPa) calculations reveal a monoclinic phase similar to the ground state structure of plutonium ({alpha}-Pu). The experimentally suggested {alpha}-U structure is found to be substantially higher in energy. The phase transition from fcc to the low symmetry structure is shown to originate from a drastic change in the nature of the electronic structure induced by the elevated pressure. A calculated volume collapse of about 25% is associated with the transition. For the low density phase, an orbital polarization correction to the local spin density (LSD) theory was applied. Gradient terms of the electron density were included in the calculation of the exchange/correlation energy and potential, according to the generalized gradient approximation (GGA). The results are consistent with a Mott transition; the 5f electrons are delocalized and bonding on the high density side of the transition and chemically inert and non-bonding (localized) on the other. Theory compares rather well with recent experimental data which implies that electron correlation effects are reasonably modeled in our orbital polarization scheme

Thermodynamics of ordered and disordered phases in the binary Mo-Ru system

We have performed ab initio calculations of the mixing enthalpy for the Mo-Ru alloy system. Both completely random alloys on the fcc, bcc, and hcp lattices as well as ordered and partially ordered structures based on the hcp lattice and a sigma phase have been examined. Further, we have performed a ground-state search for the Ru-rich region using ab initio derived effective interactions, and find a series of structures below the tie line of the simple compounds. Using the structures from this ground-state search, we are able to make an estimation of the contribution to the total energy due to ordering effects in this system. We find unusually large deviations between calculated and experimental values of the mixing enthalpy for Ru-rich hcp alloys. Our calculations indicate, in agreement with experiment, that there are ordering trends in the system. However, even under assumption of maximal order theoretical results differ substantially from the experiment. Possible reasons for the disagreement are discussed.</p

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

Quantifying the importance of orbital over spin correlations in delta-Pu within density-functional theory

Spin and orbital and electron correlations are known to be important when treating the high-temperature {delta} phase of plutonium within the framework of density-functional theory (DFT). One of the more successful attempts to model {delta}-Pu within this approach has included condensed-matter generalizations of Hund's three rules for atoms, i.e., spin polarization, orbital polarization, and spin-orbit coupling. Here they perform a quantitative analysis of these interactions relative rank for the bonding and electronic structure in {delta}-Pu within the DFT model. The result is somewhat surprising in that spin-orbit coupling and orbital polarization are far more important than spin polarization for a realistic description of {delta}-Pu. They show that these orbital correlations on their own, without any formation of magnetic spin moments, can account for the low atomic density of the {delta} phase with a reasonable equation-of-state. In addition, this unambiguously non-magnetic (NM) treatment produces a one-electron spectra with resonances close to the Fermi level consistent with experimental valence band photoemission spectra

FIRST-PRINCIPLES PHASE DIAGRAM OF THE Ce-Th SYSTEM

Actinide physics has seen a remarkable focus the last decade or so due to the combination of improved experimental diamond-anvil-cell techniques and the development of fast computers and more advanced theory. All f-electron systems are expected to have multiphase phase diagrams due to the sensitivity of the f-electron band to external influences such as pressure and temperature. For instance, compression of an f-electron metal generally causes the occupation of f-states to change due to the shift of these bands relative to others. This can in some cases, as in the Ce-Th system, cause the crystal to adopt a lower symmetry structure at elevated pressures. Here we study the phase stabilities of Ce, Th, and the Ce-Th system as a function of compression. Theoretically, both Ce and Th metals are rather well described within the DFT, although a proper treatment of the Ce-Th alloys has not yet been presented. In the present paper we revisit this problem by applying the modern theory of random alloys based on the coherent potential approximation (CPA)