Alkaline-earth metal hydrides as novel host lattices for Eu(II) luminescence

Luminescence of divalent europium has been investigated for the first time in metal hydrides. A complete solid-solution series was found for the pseudobinary system Eu(x)Sr(1-x)H(2) [a = 637.6(1) pm -12.1(3)x pm, b = 387.0(1)-6.5(2)x pm, c = 732.2(2)-10.1(4)x pm]. Europium-doped alkaline-earth hydrides Eu(x)M(1-x)H(2) (M = Ca, Sr, Ba) with a small europium concentration (x = 0.005) exhibit luminescence with maximum emission wavelengths of 764 nm (M = Ca), 728 nm (M = Sr), and 750 nm (M = Ba); i.e., the emission energy of divalent europium shows an extremely large red shift compared to the emission energies of fluorides or oxides. Theoretical calculations (LDA+U) confirm decreasing band gaps with increasing europium content of the solid solutions.     

Interaction of water‐soluble triphenylphosphines with β‐cyclodextrin: a quantum chemistry study

The interaction of β‐cyclodextrin (β‐CD) with meta‐trisulfonated triphenylphosphine derivatives bearing one or two methyl (or methoxy) groups on the aromatic rings has been investigated by PM3 calculations. The results show that phosphine molecules interact with β‐CD having either an unsubstituted sulfophenyl group or a substituted sulfophenyl group at the para and/or meta‐position. The presence of one methyl or methoxy group in the ortho‐position on each aromatic ring prevents the formation of an inclusion complex between meta‐trisulfonated triphenylphosphine derivatives and β‐CD. The deeply included phosphines in the β‐CD cavity show significant van der Waals interactions with β‐CD. These interactions are at the origin of the high association constants between these molecules and β‐CD. Phosphines exhibiting small association constants interact with β‐CD by forming H‐bonds and weak (or null) van der Waals interactions. Copyright © 2011 John Wiley & Sons, Ltd.     

Ferromagnetism,half-metallicity and spin-polarised electronic structures characterisation insights in Ca1−xTixO

ABSTRACT

In this study, we have computed the structural, electronic and half-metallic ferromagnetic properties of Ca_1?xTi_xO compounds at concentrations x?=?0.125, 0.25, 0.5 and 0.75 by employing the first-principle approaches of density functional theory. The generalised gradient approximation of Wu and Cohen (GGA-WC) is used to calculate the structural parameters, whereas the electronic structures and magnetic properties are characterised by the accurate Tran–Blaha-modi?ed Becke–Johnson potential (TB-mBJ). The lattice constant, bulk modulus and indirect gap of CaO are in good agreement with other theoretical and experimental results. The Ca_0.25Ti_0.75O at x?=?0.75 has metallic ferromagnetic nature. The Ca_0.875Ti_0.125O, Ca_0.75Ti_0.25O and Ca_0.50Ti_0.50O compounds have total magnetic moments of 2?μ_B per Ti atom with a half-metallic character, a spin polarisation of 100% and a large half-metallic gap of 1.345?eV for x?=?0.125. Therefore, the Ca_1?xTi_xO material with a low concentration of Ti is a true half-metallic ferromagnet and seems to be a promising candidate for semiconductor spintronics.     

Relaxed energetic maps of κ‐carrabiose: A DFT study

The B3LYP density function was used with the 6‐31G(d) basis set to perform relaxed energetic contour maps of the charged form of κ‐carrabiose in the gas phase and for the neutral form first in the gas phase and then by simulating the presence of water as solvent using the Onsager model. Only one starting conformation has been considered to perform all the calculations. Rigid energetic maps have been then constructed either by addition of diffuse or polarization functions to the basis set obtaining in that way 6‐31+G(d)//6‐31G(d), 6‐31+G(d,p)//6‐31G(d), and 6‐311++G(d,p)//6‐31G(d) energetic maps that have been carefully examined. The obtained structures corresponding to the lower energy conformers have been then fully optimized using different basis sets with the B3LYP method, a reversion in term of energy has been observed for the two first minima in the case of the charged disaccharide in the gas phase, this was attributed to the large grid of 30° that could lead to the exclusion of an intermediate value corresponding to the real minimum of energy. We thus suggest that after establishing potential energy maps it is essential to proceed to full optimizations of the lower energy conformers. Calculations using the more accurate correlated method MP2 with the 6‐31G(d) basis set have also been performed for conformers of the two disaccharides in the gas phase. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010     

Ab-initio study of structural,elastic, thermal,electronic and magnetic properties of quaternary Heusler alloys CoMnCrZ (Z = Al,As, Si,Ge)

First-principles approach is used to study the structural, electronic and magneticproperties of CoMnCrZ (Z = Al,Si, Ge and As) quaternary Heusler compounds, using full-potential linearized augmentedplane wave (FP-LAPW) scheme within the generalized gradient approximation (GGA). Thecomputed equilibrium lattice parameters agree well with the available theoretical data.The obtained negative formation energy shows that CoMnCrZ (Z = Al, Si, Ge, As) compounds have strongstructural stability. The elastic constants C _ij are calculatedusing the total energy variation with strain technique. The polycrystalline elastic moduli(namely: the shear modulus, Young’s modulus, Poisson’s ratio, sound velocities, Debyetemperature and melting temperature were derived from the obtained single-crystal elasticconstants. The ductility mechanism for the studied compounds is discussed via the elasticconstants C _ij . Our calculationswith the GGA approximation predict that CoMnCrGe, CoMnCrAl, CoMnCrSi and CoMnCrAs arehalf-metallic ferrimagnets (HMFs) with a half-metallic gap E _HM of 0.03 eV, 0.19 eV,0.34 eV and 0.50 eV for, respectively. We also find that the half-metallicity ismaintained on a wide range of lattice constants.