First-principles predicted low-energy structures of NaSc(BH4)4

According to previous interpretations of experimental data, sodium-scandium double-cation borohydride NaSc(BH$_4$)$_4$ crystallizes in the crystallographic space group $Cmcm$ where each sodium (scandium) atom is surrounded by six scandium (sodium) atoms. A careful investigation of this phase based on \textit{ab initio} calculations indicates that the structure is dynamically unstable and gives rise to an energetically and dynamically more favorable phase with $C222_1$ symmetry and nearly identical x-ray diffraction pattern. By additionally performing extensive structural searches with the minima-hopping method we discover a class of new low-energy structures exhibiting a novel structural motif in which each sodium (scandium) atom is surrounded by four scandium (sodium) atoms arranged at the corners of either a rectangle with nearly equal sides or a tetrahedron. These new phases are all predicted to be insulators with band gaps of $7.9-8.2$ eV. Finally, we estimate the influence of these structures on the hydrogen-storage performance of NaSc(BH$_4$)$_4$.Comment: Version publishe

Structural and electronic properties of ScnOm (n=1~3, m=1~2n) clusters: Theoretical study using screened hybrid density functional theory

The structural and electronic properties of small scandium oxide clusters ScnOm (n = 1 - 3, m = 1 - 2n) are systematically studied within the screened hybrid density functional theory. It is found that the ground states of these scandium oxide clusters can be obtained by the sequential oxidation of small "core" scandium clusters. The fragmentation analysis demonstrates that the ScO, Sc2O2, Sc2O3, Sc3O3, and Sc3O4 clusters are especially stable. Strong hybridizations between O-2p and Sc-3d orbitals are found to be the most significant character around the Fermi level. In comparison with standard density functional theory calculations, we find that the screened hybrid density functional theory can correct the wrong symmetries and yield more precise description for the localized 3d electronic states of scandium.Comment: 8 figure

NLTE study of scandium in the Sun

We investigate the formation of neutral and singly ionized scandium lines in the solar photospheres. The research is aimed derive solar $\log gf\epsilon_{\odot}$(Sc) values for scandium lines, which will later be used in differential abundance analyses of metal-poor stars. Extensive statistical equilibrium calculations were carried out for a model atom, which comprises 92 terms for \ion{Sc}{i} and 79 for \ion{Sc}{ii}. Photoionization cross-sections are assumed to be hydrogenic. Synthetic line profiles calculated from the level populations according to the NLTE departure coefficients were compared with the observed solar spectral atlas. Hyperfine structure (HFS) broadening is taken into account. The statistical equilibrium of scandium is dominated by a strong underpopulation of \ion{Sc}{i} caused by missing strong lines. It is nearly unaffected by the variation in interaction parameters and only marginally sensitive to the choice of the solar atmospheric model. Abundance determinations using the ODF model lead to a solar Sc abundance of between $\log\epsilon_\odot = 3.07$ and 3.13, depending on the choice of $f$ values. The long known difference between photospheric and meteoritic scandium abundances is confirmed for the experimental $f$-values.Comment: 10 pages, 6 figures, A&A accepte

Vibrational spectroscopic force field studies of dimethyl sulfoxide and hexakis(dimethyl sulfoxide)scandium(III) iodide, and crystal and solution structure of the hexakis(dimethyl sulfoxide)scandium(III) ion

Hexakis(dimethyl sulfoxide) scandium(III) iodide, [Sc(OS(CH3)(2))(6)]I-3 contains centrosymmetric hexasolvated scandium(III) ions with an Sc-O bond distance of 2.069(3) Angstrom. EXAFS spectra yield a mean Sc-O bond distance of 2.09(1) Angstrom for solvated scandium(III) ions in dimethyl sulfoxide solution, consistent with six-coordination. Raman and infrared absorption spectra have been recorded, also of the deuterated compound, and analysed by means of normal coordinate methods, together with spectra of dimethyl sulfoxide. The effects on the vibrational spectra of the weak intermolecular C-H...O interactions and of the dipole dipole interactions in liquid dimethyl sulfoxide have been evaluated, in particular for the S O stretching mode. The strong Raman band at 1043.6 cm(-1) and the intense IR absorption at 1062.6 cm(-1) have been assigned as the S-O stretching frequencies of the dominating species in liquid dimethyl sulfoxide, evaluated as centrosymmetric dimers with antiparallel polar S-O groups. The shifts of vibrational frequencies and force constants for coordinated dimethyl sulfoxide ligands in hexasolvated trivalent metal ion complexes are discussed. Hexasolvated scandium( III) ions are found in dimethyl sulfoxide solution and in [Sc(OSMe2)(6)]I-3. The iodide ion dipole attraction shifts the methyl group C H stretching frequency for (S-)C-H...I- more than for the intermolecular (S-)C-H...O interactions in liquid dimethyl sulfoxide

Evidence against anomalous compositions for giants in the Galactic Nuclear Star Cluster

Very strong Sc I lines have been found recently in cool M giants in the Nuclear Star Cluster in the Galactic Center. Interpreting these as anomalously high scandium abundances in the Galactic Center would imply a unique enhancement signature and chemical evolution history for nuclear star clusters, and a potential test for models of chemical enrichment in these objects. We present high resolution K-band spectra (NIRSPEC/Keck II) of cool M giants situated in the solar neighborhood and compare them with spectra of M giants in the Nuclear Star Cluster. We clearly identify strong Sc I lines in our solar neighborhood sample as well as in the Nuclear Star Cluster sample. The strong Sc I lines in M giants are therefore not unique to stars in the Nuclear Star Cluster and we argue that the strong lines are a property of the line formation process that currently escapes accurate theoretical modeling. We further conclude that for giant stars with effective temperatures below approximately 3800 K these Sc I lines should not be used for deriving the scandium abundances in any astrophysical environment until we better understand how these lines are formed. We also discuss the lines of vanadium, titanium, and yttrium identified in the spectra, which demonstrate a similar striking increase in strength below 3500 K effective temperature.Comment: 11 pages, 6 figures, accepted for publication in Ap

R and D and evaluation of a lightweight, high strength magnesium alloy Quarterly report, 1 Feb. - 1 May 1969

Light weight high strength magnesium scandium allo

Laboratory oscillator strengths of Sc I in the near-infrared region for astrophysical applications

Context. Atomic data is crucial for astrophysical investigations. To understand the formation and evolution of stars, we need to analyse their observed spectra. Analysing a spectrum of a star requires information about the properties of atomic lines, such as wavelengths and oscillator strengths. However, atomic data of some elements are scarce, particularly in the infrared region, and this paper is part of an effort to improve the situation on near-IR atomic data. Aims. This paper investigates the spectrum of neutral scandium, Sc i, from laboratory measurements and improves the atomic data of Sc i lines in the infrared region covering lines in R, I, J, and K bands. Especially, we focus on measuring oscillator strengths for Sc i lines connecting the levels with 4p and 4s configurations. Methods. We combined experimental branching fractions with radiative lifetimes from the literature to derive oscillator strengths (f - values). Intensity-calibrated spectra with high spectral resolution were recorded with Fourier transform spectrometer from a hollow cathode discharge lamp. The spectra were used to derive accurate oscillator strengths and wavelengths for Sc i lines, with emphasis on the infrared region. Results. This project provides the first set of experimental Sc i lines in the near-infrared region for accurate spectral analysis of astronomical objects. We derived 63 log(g f ) values for the lines between 5300{\AA} and 24300{\AA}. The uncertainties in the f -values vary from 5% to 20%. The small uncertainties in our values allow for an increased accuracy in astrophysical abundance determinations.Comment: Accepted on 25 August 2015 by A&

The loss of anisotropy in MgB2 with Sc substitution and its relationship with the critical temperature

The electrical conductivity anisotropy of the sigma-bands is calculated for the (Mg,Sc)B2 system using a virtual crystal model. Our results reveal that anisotropy drops with relatively little scandium content (< 30%); this behaviour coincides with the lowering of Tc and the reduction of the Kohn anomaly. This anisotropy loss is also found in the Al and C doped systems. In this work it is argued that the anisotropy, or 2D character, of the sigma-bands is an important parameter for the understanding of the high Tc found in MgB2