Ab initio modeling of oxygen impurity atom incorporation into uranium mononitride surface and subsurface vacancies

The incorporation of oxygen atoms has been simulated into either nitrogen or uranium vacancy at the UN(001) surface, sub-surface or central layers. For calculations on the corresponding slab models both the relativistic pseudopotentials and the method of projector augmented-waves (PAW) as implemented in the VASP computer code have been used. The energies of O atom incorporation and solution within the defective UN surface have been calculated and discussed. For different configurations of oxygen ions at vacancies within the UN(001) slab, the calculated density of states and electronic charge re-distribution was analyzed. Considerable energetic preference of O atom incorporation into the N-vacancy as compared to U-vacancy indicates that the observed oxidation of UN is determined mainly by the interaction of oxygen atoms with the surface and sub-surface N vacancies resulting in their capture by the vacancies and formation of O-U bonds with the nearest uranium atoms. Keywords: Density functional calculations, uranium mononitride, surface, defects, N and U vacancie

Calculations for antiferrodistortive phase of SrTiO3 perovskite: hybrid density functional study

The electronic and atomic structure of SrTiO3 crystals below the antiferrodistortive phase transition observed at 105 K is calculated using the hybrid B3PW functional as implemented in the ab initio CRYSTAL-2003 computer code. Such a combination of non-local exchange and correlation permits the calculation for the first time of the TiO6 octahedron rotational angle and the ratio c/a of tetragonal lattice constants in excellent agreement with experimental data. The level splitting of the bottom of the conduction band is found to be very small, <1 meV. The predicted phase-transition induced change of the optical gap from indirect to direct is confirmed by experimental photoconductivity data

A Test of the Expectations Hypothesis in Very Short-term International Rates in the Presence of Preferred Habitat for Liquidity

This study incorporates year-end and quarter-end preferences for liquidity and other calendar-time effects into the test of the expectations hypothesis (EH) in the very short-term LIBOR (maturities of one month and shorter) in seven major world currencies. The calendar-time effects are found to alter long-term relations between very short-term rates in these currencies. These effects alone are not responsible for the rejection of the EH in the data, as it is rejected in most of the cases even after appropriate controls are introduced. However, such effects are capable of causing the EH to be rejected and should be controlled for when testing the EH in very short-term rates

The Year-end Effect in Money Market Yields: Beyond One Month and Beyond the Crisis

U.S. money market yields up to one month have shown changes consistent with year-end liquidity preferences. I find that three- and six-month negotiable certificate of deposit (CD), Eurodollar deposit (ED), and banker’s acceptance (BA) yields are also affected by year-end liquidity preferences. Two- and three-month financial commercial paper (CP) yield changes are less pronounced. Banks – CD, ED, and BA issuers – have increased year-end liquidity needs, unlike finance companies – predominant CP issuers. The year-end effect disappears after the 2007-2008 crisis as depositories’ cash holdings increase. CD, ED, and CP yields diverge post-crisis, suggesting that investors no longer consider them close substitutes

Diffusion-controlled annihilation A+B→0A + B \to 0: The growth of an AA particle island from a localized AA-source in the BB particle sea

We present the growth dynamics of an island of particles $A$ injected from a localized $A$-source into the sea of particles $B$ and dying in the course of diffusion-controlled annihilation $A+B\to 0$. We show that in the 1d case the island unlimitedly grows at any source strength $\Lambda$, and the dynamics of its growth {\it does not depend} asymptotically on the diffusivity of $B$ particles. In the 3d case the island grows only at $\Lambda > \Lambda_{c}$, achieving asymptotically a stationary state ({\it static island}). In the marginal 2d case the island unlimitedly grows at any $\Lambda$ but at $\Lambda < \Lambda_{*}$ the time of its formation becomes exponentially large. For all the cases the numbers of surviving and dying $A$ particles are calculated, and the scaling of the reaction zone is derived.Comment: 5 REVTEX pages, no figure

Diffusion-controlled death of AA-particle and BB-particle islands at propagation of the sharp annihilation front A+B→0A + B \to 0

We consider the problem of diffusion-controlled evolution of the system $A$-particle island - $B$-particle island at propagation of the sharp annihilation front $A+B\to 0$. We show that this general problem, which includes as particular cases the sea-sea and the island-sea problems, demonstrates rich dynamical behavior from self-accelerating collapse of one of the islands to synchronous exponential relaxation of the both islands. We find a universal asymptotic regime of the sharp front propagation and reveal limits of its applicability for the cases of mean-field and fluctuation fronts.Comment: 4 revtex pages, 1 jpg figure. Submitted to Phys. Rev.

First principles calculations of oxygen adsorption on the UN (001) surface

Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. The basic properties of O atoms adsorbed on the UN(001) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized atomic orbitals.Comment: 9 page

Comparative theoretical study of the Ag-MgO (100) and (110) interfaces

We have calculated the atomic and electronic structures of Ag-MgO(100) and (110) interfaces using a periodic (slab) model and an ab initio Hartree-Fock approach with a posteriori electron correlation corrections. The electronic structure information includes interatomic bond populations, effective charges, and multipole moments of ions. This information is analyzed in conjunction with the interface binding energy and the equilibrium distances for both interfaces for various coverages. There are significant differences between partly covered surfaces and surfaces with several layers of metal, and these can be understood in terms of electrostatics and the electron density changes.For complete monolayer (1:1) coverage of the perfect MgO(100) surface, the most favorable adsorption site energetically for the Ag atom is above the surface oxygen. However, for partial (1:4) coverage of the same surface, the binding energies are very close for all the three likely adsorption positions (Ag over O, Ag over Mg, Ag over a gap position),For a complete (1:1) Ag monolayer coverage of the perfect MgO(110) interface, the preferable Ag adsorption site is over the interatomic gap position, whereas for an Ag bilayer coverage the preferred Ag site is above the subsurface Mg2+ ion (the bridge site between two nearest surface O2- ions). In the case of 1:2 layer coverage, both sites are energetically equivalent. These two adhesion energies for the (110) substrate are by a factor of two to three larger than over other possible adsorption sites on perfect(110) or (100) surfaces.We compare our atomistic calculations for one to three Ag planes with those obtained by the shell model for 10 Ag planes and the Image Interaction Model addressing the case of thick metal layers. Qualitatively, our ab initio results agree well with many features of these models. The main charge redistributions are well in line with those expected from the Image Model. There is also broad agreement in regard to orders of magnitude of energies. (C) 1999 Elsevier Science B.V. All rights reserved