Synchrotron radiation study of interconfigurational 5d-4f luminescence of Pr3+ in KLuP2O7

The double phosphate KLuP2O7 doped with Pr 3+ ions was prepared by solid-state reaction. The material obtained was characterized by powder X-ray diffraction. The luminescence spectroscopy and the excited state dynamics of this material were studied upon excitation with VUV synchrotron radiation. The 5d-4f emission of Pr3+ upon both direct and band gap excitation was detected and assigned. The decay kinetics of the Pr3+ 5d-4f emission is characterized by a decay time of about 20 ns and is nearly temperature independent within the range 8-300 K. Both dynamics and energy transfer peculiarities revealed in the study suggested good potentials for application of KLuP2O7:Pr3+ as a fast scintillator material. © 2014 Verlag der Zeitschrift für Naturforschung, Tübingen

Exact inflationary solutions

We present a new class of exact inflationary solutions for the evolution of a universe with spatial curvature, filled with a perfect fluid, a scalar field with potential $V_{\pm}(\phi)=\lambda(\phi^2\pm\delta^2)^2$ and a cosmological constant $\Lambda$. With the $V_+(\phi)$ potential and a negative cosmological constant, the scale factor experiments a graceful exit. We give a brief discussion about the physical meaning of the solutions.Comment: 10 pages, revtex file, 6 figures included with epsf. To be published in IJMP-

The effect of cation substitution on the local coordination of protons in Ba2In1.85M0.15O6H2 (M = In, Ga, Sc and Y)

We report on an investigation of the local structure and vibrational dynamics in the brownmillerite-based proton conductors Ba2In1.85M0.15O6H2 with M = In, Ga, Sc and Y. The aim is to determine the effect of the cation (M) substitution on the local coordination environment of the protons. The techniques used are infrared spectroscopy and inelastic neutron scattering. The materials are characterized by two main types of proton sites, denoted as H (1) and H(2), which are featured by different local structures. We establish that the relative population of these two proton sites varies as a function of M. Specifically, it is found that, with respect to Ba2In2O6H2, the relative population of H(1) protons increases upon the substitution of In with any of the three different cations. The strongest effect is observed for M = Ga and Sc, whereas the effect observed for M = Y is minor. This new insight motivates efforts to unravel the mobility of the two types of protons, since then cation modification would offer a rational route for improving the proton conductivity of these types of materials

NIR-emission from Yb(III)- and Nd(III)-based complexes in the solid state sensitized by a ligand system absorbing in a broad UV and visible spectral window

In this contribution, we present the synthesis, characterization and spectroscopic investigation of the heteroleptic (R,R)-YbL1(tta) and (R,R)-NdL1(tta) complexes (with tta = 2-thenoyltrifluoroacetonate and L1 = N,N'-bis(2-(8-hydroxyquinolinate)methylidene)-1,2-(R,R or S,S)-cyclohexanediamine) in the solid state. The f-f metal-centered NIR luminescence emission of Nd(III) and Yb(III) is efficiently sensitized by both chromophoric ligands in a very broad range of wavelengths [from 250 to 600 nm, in the case of Nd(III) and from 250 to 650 nm, for Yb(III)]. A possible energy transfer mechanism is proposed: for (R,R)-NdL1(tta) complex a classical Ligand-to-Metal Energy Transfer (LMET) mechanism (antenna effect) is suggested, whilst in the case of the (R,R)-YbL1(tta) complex, the presence of a ligand-to-metal charge transfer (LMCT) state determines the sensitization of Yb(III) luminescence. We propose that this level is populated by the singlet and triplet excited states belonging to pi -> pi* and n -> pi* transitions of both ligands and it can transfer the excitation energy to F-2(5/2)

Lanthanide-Based Complexes Containing a Chiral trans-1,2-Diaminocyclohexane (DACH) Backbone: Spectroscopic Properties and Potential Applications

In this minireview, we give an overview on the use of the chiral molecule trans-1,2-diaminocyclohexane (DACH) in several fields of application. This chiral backbone is present in a variety of metal complexes which are employed in (enantioselective) catalysis, chiral discrimination, molecular recognition and supramolecular chemistry. Metal extraction and biochemical and pharmaceutical applications also use the DACH molecule. This contribution is particularly focused on the interesting chemical-physical properties discussed so far in the literature concerning lanthanide-based complexes containing chiral ligands characterized by the presence of DACH in the structure. In particular, the interconnection between luminescence (total and circularly polarized), structure and thermodynamics of Eu(III), Tb(III) and Sm(III) complexes will be discussed also in light of their use as optical or chiroptical probes for the sensing of important analytes dissolved in aprotic and protic polar solvents. Several complexes show potential interest in the solid state as phosphors for light emitting devices or for the detection of volatile organic compounds

Tunable emission from silico-carnotite type double silicates doped with Tb^3+ and Eu^3+

Double silicates with the silico-carnotite orthorhombic structure and co-doped with Tb3+ and Eu3+ have been prepared by solid-state reaction. Room temperature luminescence spectra and decay kinetics have been measured and analysed. Upon UV excitation at 378 nm, the emission colour varies from red to pinkish, depending on the doping level. The resulting colour can be adjusted by controlling the Tb3+/Eu3+ concentration ratio. Control of the doping leads to close-to-white emission in some of the analysed samples upon excitation in the wavelength region useful for LED lightin

The effects of Non-Gaussian initial conditions on the structure and substructure of Cold Dark Matter halos

We study the structure and substructure of halos obtained in N-body simulations for a Lambda Cold Dark Matter (LCDM) cosmology with non-Gaussian initial conditions (NGICs). The initial statistics are lognormal in the gravitational potential field with positive (LNp) and negative (LNn) skewness; the sign of the skewness is conserved by the density field, and the power spectrum is the same for all the simulations. Our aim is not to test a given non-Gaussian statistics, but to explore the generic effect of positive- and negative-skew statistics on halo properties. From our low-resolution simulations, we find that LNp (LNn) halos are systematically more (less) concentrated than their Gaussian counterparts. This result is confirmed by our Milky Way- and cluster-sized halos resimulated with high-resolution. In addition, they show inner density profiles that depend on the statistics: the innermost slopes of LNp (LNn) halos are steeper (shallower) than those obtained from the corresponding Gaussian halos. A subhalo population embedded in LNp halos is more susceptible to destruction than its counterpart inside Gaussian halos. On the other hand, subhalos in LNn halos tend to survive longer than subhalos in Gaussian halos. The spin parameter probability distribution of LNp (LNn) halos is skewed to smaller (larger) values with respect to the Gaussian case. Our results show how the statistics of the primordial density field can influence some halo properties, opening this the possibility to constrain, although indirectly, the primordial statistics at small scale.Comment: 15 pages, 8 figures. Slight corrections after referee report. To appear in ApJ, v598, November 20, 200

Temperature dependence and temporal dynamics of Mn2+ upconversion luminescence sensitized by Yb3+ in codoped LaMgAl11O19

A detailed spectroscopic study of the upconversion properties in Mn2+-Yb3+ codoped LaMgAl11O19 is presented. Pulsed and continuous-wave infrared excitation in the 2F7/2--2F5/2 Yb3+ absorption peaks induces broad Mn2+ green emission at 19450 cm-1, which is assigned to the 4T1--6A1 transition in tetrahedral Mn2+ and sharp peaks associated with Yb3+-pairs luminescence. Both emissions have very different temporal evolution and can be separated by time-resolved spectroscopy. Among the different concentrations under investigation, the 2%Mn2+-5%Yb3+ codoped system presents the highest upconversion efficiency. The corresponding emission remains visible to the naked eye up to 650 K. The time dependence of the Mn2+ luminescence upon Yb3+ excitation shows distinct behaviors for different doping concentrations. The temporal evolution of the intensity for the diluted system doped with 2%Mn2+ and 5%Yb3+ together with the pure manganese compound doped with 1%Yb3+, as well as the temperature dependence of the upconversion emission intensity and lifetime are relevant to identify the underlying upconversion mechanisms. We show that the main processes responsible for upconversion in this doubly transition-metal rare-earth doped oxide are both ground-state absorption (GSA)/excited-state absorption and GSA/energy-transfer upconversion. An analysis of these processes yielding highly efficient luminescence is discussed on the basis of crystal structure and dopants.This work was financially supported by the Spanish Ministerio de Ciencia e Innovación (Project No. MAT2008- 06873-C02-01/MAT) and the MALTA-Consolider Ingenio 2010 (Reference No. CSD2007-00045). R.M.-R. thanks the Spanish MEC for a FPI research grant (Reference No. BES-2006-13359)

Spontaneous self-assembly of an unsymmetric trinuclear triangular copper(II) pyrazolate complex, [Cu3(μ3-OH)(μ-pz) 3(MeCOO)2(Hpz)] (Hpz = pyrazole). Synthesis, experimental and theoretical characterization, reactivity, and catalytic activity

The almost quantitative formation of the triangular trinuclear copper derivative [Cu3(μ3-OH)(μ-pz)3(MeCOO) 2(Hpz)] (1) (Hpz = pyrazole), has been simply achieved by adding Hpz to an ethanol solution of Cu(MeCOO)2·H2O. An X-ray molecular structure determination shows that 1 is completely unsymmetric and that trinuclear units result assembled in an extended bidimensional network formed through acetate bridges and hydrogen bonds. EPR and magnetic measurements are consistent with the presence of a single unpaired electron. Theoretical density functional calculations carried out for S = 1/2 provide a thorough description of the electronic structure of 1, allowing a detailed assignment of its UV-vis absorption spectrum. Compound 1 reacts with MeONa, yielding [Cu 3(μ3-OH)(μ-pz)3(MeCOO)(MeO)(Hpz)] (2) and [Cu3(μ3-OH)(μ-pz)3(MeO) 2(Hpz)] (3) through the substitution of one and two acetate ions, respectively, with MeO- ion(sS). The spontaneous self-assembly of the triangular trinuclear Cu3 moiety seems to occur only with pyrazole as can be inferred by the results obtained in the reactions of copper(II) acetate with some substituted pyrazoles leading to the formation of mononuclear [Cu(MeCOO)2(L)2] (4-8) and dinuclear [Cu(MeCOO) 2(L)]2 (9-11) (L = substituted pyrazole) compounds. Also the presence of acetate ions seems to play a leading role in determining the formation of the trinuclear triangular arrangement, as indicated by the formation of a mononuclear derivative, [Cu(CF3COO) 2(Hpz)]2 (compound 12), in the reaction of copper(II) trifluoroacetate with pyrazole. Compounds 1-3, as well as some other mono- and dinuclear copper(II)-substituted pyrazole complexes, have been tested as catalyst precursors in cyclopropanation reaction, observing the formation of products in a syn:anti ratio opposite that normally reported