Red-shift in the photostimulation of the X-ray storage phosphor RbBr:Ga+

Abstract

By means of magnetic circular dichroism of the optical absorption and photostimulated luminescence (PSL) the X-ray induced formation of F_A and F centres in RbBr:(Ga⁺, Li⁺) was investigated. It turnes out that RbBr:Ga⁺ co-doped with 1% Li⁺ in the melt reveals the largest red-shift of the PSL excitation bands to 790 nm, whereby the F_A to F ratio increases up to about 10% with decreasing X-ray dose. This is more than statistically expected (6%). High X-ray doses destroy F_A centres. However, up to 15% of the simultaneously generated F centres could be converted into the F_A species by appropriate bleaching with 633 nm light into the F centre absorption band.     

EPR and optical absorption of manganese doped BaF2 and SrF2

Abstract

Mn⁺ ions in off-centre position along [100] have been produced in BaF₂:Mn by X-irradiation at LNT. Their EPR spectra are characterized by g-2. 0107. D = 265.8·10^?4cm^?1. A = 122.9·10^?4cm^?11 and a superhyperfine structure arising from 8 surrounding F^? nuclei. In the optical absorption spectrum they show up by a band at 411 nm. This behaviour is compared with the results found for SrF₂:Mn. After X-irradiation at room temperature beside a different Mn⁺ centre two species of Mn⁰ appear in non-cubic position. Both interact dominantly with two F^? neighbours. Possible models for these species are discussed.     

Raman scattering investigations of KY3F10

Single crystals of the fluoride compound KY₃F₁₀ (O_h⁵) were studied by Raman scattering from 40 to 950 K. Group theory analysis predicts 3A_1g + 4E_g + 6F_2g Raman-active modes, but the experimental spectra show two F_2g modes missing. Over the whole temperature range the frequency shifts are negligible whereas the line widths show a strong increase with temperature. Both reversible and irreversible line width behaviour are exhibited for different temperature runs, indicating a complex microscopic phenomenon underlying the creation of defects responsible for these line widths and their interaction with the different phonon modes. An approximate activation energy for defect creation of ΔE ≈︁ 0.3 eV can be obtained from the temperature behaviour of the line widths. This activation energy may be connected with the high-temperature ionic conduction mentioned previously for this crystal.     

Investigation of the dynamical behaviour of the FH(CN−) centre in KCl with temperature dependent endor spectroscopy

Abstract

The temperature dependence of the electron nuclear double resonance (ENDOR) spectra of F_H(CN^?) centres in KCl was investigated in the temperature range between 10–220 K. At the lowest temperature of 10 K only one CN^? orientation with respect to the F centre electron is present, in which the nitrogen is thought to be nearer to the F-electron than the carbon. With the very small thermal activation energy of 2.9 meV the opposite orientation is occupied. The superhyperfine interactions of those first shell K nuclei nearest to CN^? and of the ¹³C interaction of the CN^? molecule are strongly temperature dependent between 10 and 60 K, following an exponential law with a thermal activation energy of 4.2 meV. It is assumed that a soft local mode involving those two nearest K nuclei and the CN^? is causing the strong temperature dependence. The shf interactions of ¹⁴N nuclei have not been seen, probably because of the dynamical effects.     

Behaviour of F and Fz Centres Under Thermal Stimulation in KCl:Eu2☎ Irradiated with Ionizing and UV Radiation

The optical absorption (OA) of F and F_z, centres in beta-and UV-irradiated KCl: Eu^2? have been studied. The spectra measured at room temperature and during the subsequent heatings up to 600 K, were analyzed by a deconvolution procedure. The OA bands of the F and F_z centres are well described respectively by asymmetric and symmetric gaussiane with parameters that are linearly dependent on the temperature. The thermal stability of the F_z centres correlates with the low-temperature thermostimulated luminescence (TL) peaks. The stability of the F centres is determined at least by two processes. Part of the F centres is destroyed together with the F_z centres. The remaining ones are destroyed during further heating up to 470 K, correlating with the TL peak at 425 K (at heating rate of 0.1 K/s).     

Theoretical calculations of the optical band positions and spin-Hamiltonian parameters for Yb at the tetragonal Y site of KY3F10 crystal

The six optical band positions and six spin-Hamiltonian parameters [g factors g_∥, g_⊥ and hyperfine structure constants A_∥(¹⁷¹Yb³⁺), A_⊥(¹⁷¹Yb³⁺), A_∥(¹⁷³Yb³⁺), A_⊥(¹⁷³Yb³⁺)] for Yb³⁺ ion at the tetragonal Y³⁺ site of KY₃F₁₀ crystal are calculated from a diagonalization (of energy matrix) method. In the method, the Hamiltonian of energy matrix contains the free-ion, crystal-field interaction, Zeeman (or magnetic) interaction and hyperfine interaction terms and so a 14×14 complete energy matrix for 4f¹³ ion in tetragonal crystal-field and under an external magnetic field is constructed. Diagonalizing the energy matrix, these optical and EPR spectral data are calculated together and the calculated results are in reasonable agreement with the experimental values. The signs of hyperfine structure constants A_∥, A_⊥ for the isotopes ¹⁷¹Yb³⁺ and ¹⁷³Yb³⁺ in KY₃F₁₀ are suggested. The results are discussed.     

Phase transitions in PbZrxTi1_XO3 with up to 3% Ti content

Abstract

On the basis of investigations of dielectric, pyroelectric and piezoelectric properties and by differential thermal analysis, the existence of a ferroelectric phase and of A ? F and F ? P phase transitions in Pb/Zr _x Ti_1-x /O₃ samples, containing up to 3% Ti, were determined.

It has been shown that a ferroelectric state appears despite the lack of doping and despite the lack of external factors. The introduction of Ti causes a lowering of the energy barrier between the A and F states. The results verify a cluster mechanism for the appearance of an F state in the antiferroelectric PbZrO₃ matrix.     

Phonon-assisted luminescence anomalies in Eu2+ doped Ca1-xSrxF2 mixed crystals

Abstract

With increasing X on Ca_1-xSr_xF₂ mixed crystals doped with Eu²⁺ (4f⁶5d) ions, the absorption peak shifted linearly to that of SrF₂:Eu, while the luminescence one moved parabolically with a minimum at around x=0.5. The linewidth broadened nearly twice as large as that of CaF₂ in the vicinity of x=0.5 and subsequently renarrowed for x > 0.5. The temperature dependences of the luminescence intensity and life time revealed that the nonradiative activation energy has a minimum of 0.40 eV around x=0.5. From the calculated result of the lineshape, these non-linear behaviors against x were explained by adjusting the electron-phonon coupling strength.     

DFT study of boron trichloride adsorption on the surface of Al12N12 nanocluster

In the present study, ability of Al₁₂N₁₂ nanocluster as a new adsorbent for boron trichloride is studied by using density functional theory (DFT) calculations. Two distinct relaxed geometries of Al₁₂N₁₂-BCl₃ complex are located. The dominant configuration (B) involves chemisorption of BCl₃ on aluminum nitride nanocluster with an adsorption energy of ?303 kJ/mol compared to ?33 kJ/mol for a less favourable configuration A (based on wB97XD functional). The enthalpy and Gibbs free energy of interaction for each relaxed was also analysed for better understanding of the thermochemistry of adsorption process. The charge transfer analysis reveals opposing trend in both configurations. Configuration A showed transfer of charge from BCl₃ to nanocluster (+0.123 e), whereas reverse direction of charge transfer was found for the other configuration (?0.083 e). Furthermore, the frontier molecular orbital as well as densities of states of all systems are analysed to follow the changes in the electronic structure of Al₁₂N₁₂ upon adsorption of BCl₃.     

Density functional theory study on LaNi4.5Al0.5 hydride phase： electronic properties and sites occupation＊

In this paper the crystal structure, electronic structure and hydrogen site occupation of LaNi4.5Al0.5Hy hydride phase （y = 5.0, 6.0） have been investigated by using full-potential linearized augmented plane wave method. The hydrogen atoms were found to prefer the 6m, 12o and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion, the total density of states at EF increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, H plays a dominant role in the stability of LaNi4.5Al0.5 hydride phase. The smaller the shift of EF towards the higher energy region, the more stable the compounds will be. The obtained results are compared with experimental data and discussed in the light of previous works.     

Conformational analysis of <Emphasis Type="Italic">o</Emphasis>-allylphenol by density functional and IR spectroscopy methods

The two-dimensional cyclic potential energy surfaces for internal rotation of the allyl substituent and its vinyl fragment in o-allylphenol (o-APh) depending on the OH group orientation relative to the allyl substituent were constructed by a B3LYP/6-31G method. It is shown that o-APh exists in the gas phase as a mixture of eight non-planar rotamers (A, B, C, D, E, F, G, and H) and their eight optical isomers (A ₁, B ₁, C ₁, D ₁, E ₁, F ₁, G ₁, and H ₁). An intramolecular H-bond (IHB) O–H...π occurs only in four rotamers (A, B, A ₁, and B ₁). The content of such rotamers in the gas phase is 47.2% (as calculated by the B3LYP/cc-pVTZ method). Taking into account the solvation effect in the polarizable continuum model (PCM) for a solution of o-APh in cyclohexane decreases the total content of rotamers with an IHB (A and B) to 37.7%. The ratio of rotamers with OH groups bonded by an IHB and with free OH groups that is predicted theoretically agrees with the value measured experimentally from IR spectra of o-APH in CCl₄ solution.     

Oscillator strength of F2 − colour centres in LiF crystal

The absorption cross-section integral and the oscillator strength of the 960 nm absorption band due to F₂ ^– colour centres in LiF crystal is determined at room temperature from the absorption cross-section spectrum of the F₂ ^– centres obtained from saturable absorption studies. A comparison with previous results is made.     

Vibrational properties of the F A (Li+) center in alkali halides

Abstract

The on- or off-axis behavior and the vibrational properties of the F _A (Li⁺) center are investigated in several alkali halides by means of polarized resonant Raman scattering. The observed Raman modes are interpreted and classified according to their nature and frequency. A comparison between on- and off-axis systems and between the vibrational modes of the isolated Li⁺ and the F _A (Li⁺) center reveals a displacement of the Li⁺ equilibrium position parallel to the F _A (Li⁺) defect axis and, due to the small impurity size, away from the adjacent F center.     

Anomalous heat capacity of Agx and the nonlinear temperature dependence of the formation energy of Frenkel defects

Abstract

The nonlinear decrease of Gibbs free energy (g_F) for the formation of Frenkel defects in Agx accounts for the anomalous increase of electrical conductivity and self-diffusion in this system. Using an analytical expression for g_F(T) the excess heat capacity for Frenkel defects is calculated. A comparison with experimental data indicates that all the anomalies of heat capacity at high temperature is not accounted for. A contribution from Schottky defects is thus probable.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

Organizational dynamics of formation of the color center saddle point in KCl: Li

Emission from the relaxed saddle point configuration of the F_A(II) color center of KCl: Li is delayed by over 200 psec. The intermediate state initially formed following optical excitation is suggested to be the relaxed F_A(I) configuration, and the delay is associated with the mean time for first passage towards the F_A(II) saddle point configuration.     

Optical spectroscopy of Mn2+ ions in CaCl2 single crystals

Abstract

In the present investigation the excitation and fluorescence spectra and lifetimes of Mn²⁺ ions in calcium chloride, for various manganese concentrations and sample temperatures have been studied for the first time. The fluorescence spectrum consists of an asymmetric broad band, which upon lowering the sample temperature, shifts its maximum from 580 nm at 300 K to 596 nm at 11 K. This luminescence band was associated with the ⁴T_lg(⁴G)→⁶A_lg(⁶S) spin-forbidden transition in the manganese ions occupying Ca-sites in the lattice of CaCl₂. The excitation spectrum of the Mn²⁺ fluorescence revealed the features of manganese ions in octahedral coordination and consisted of nine excitation peaks which were associated with Mn²⁺-crystal-field-sensitive transitions. A crystal field analysis of the wavelength positions of these transitions by means of the model developed by Curie et al. allowed us to determine the magnitude of the cubic field splitting 10Dq, the reduced Racah parameter B', the Koide-Pryce covalency parameter ε and the spin transfer coefficients f _[sgrave] and f _σ. From the measurement of the temperature dependence of the Mn²⁺ fluorescence lifetime, we have also obtained information about the different mechanisms which are involved in the relaxation of excited Mn²⁺ ions in this host crystal in the temperature range (11–300 K).     

Single-particle thermal diffusion of charged colloids: Double-layer theory in a temperature gradient

The double-layer contribution to the single-particle thermal diffusion coefficient of charged, spherical colloids with arbitrary double-layer thickness is calculated and compared to experiments. The calculation is based on an extension of the Debye-Hückel theory for the double-layer structure that includes a small temperature gradient. There are three forces that constitute the total thermophoretic force on a charged colloidal sphere due to the presence of its double layer: i) the force F _W that results from the temperature dependence of the internal electrostatic energy W of the double layer, ii) the electric force F _el with which the temperature-induced non-spherically symmetric double-layer potential acts on the surface charges of the colloidal sphere and iii) the solvent-friction force F _sol on the surface of the colloidal sphere due to the solvent flow that is induced in the double layer because of its asymmetry. The force F _W will be shown to reproduce predictions based on irreversible-thermodynamics considerations. The other two forces F _el and F _sol depend on the details of the temperature-gradient-induced asymmetry of the double-layer structure which cannot be included in an irreversible-thermodynamics treatment. Explicit expressions for the thermal diffusion coefficient are derived for arbitrary double-layer thickness, which complement the irreversible-thermodynamics result through the inclusion of the thermophoretic velocity resulting from the electric- and solvent-friction force.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Mexiletine

The 60 MHz ¹H NMR spectra of mexiletine, 1-(2,6-dimethylphenoxy)-2-propanamine, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent, tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium(III), 2, Eu(FOD)₃, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)-d-camphorato]europium(III), 3, Eu(FACAM)₃, and tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 4, Eu(HFC)₃. Substantial lanthanide-induced shifts were seen for the proton signals of 1 with each reagent. Appreciable enantiomeric shift differences were seen for both methyl signals and for each of the CH₂CH proton signals using 3 and 4 that should permit direct determinations of enantiomeric excess for samples of 1. A predominant conformation for 1 is suggested based on observed splittings of the CH₂ proton signals and their relative lanthanide-induced shifts.     

SAFT-γ force field for the simulation of molecular fluids: 8. Hetero-segmented coarse-grained models of perfluoroalkylalkanes assessed with new vapour–liquid interfacial tension data

ABSTRACT

The air–liquid interfacial behaviour of linear perfluoroalkylalkanes (PFAAs) is reported through a combined experimental and computer simulation study. The surface tensions of seven liquid PFAAs (perfluorobutylethane, F₄H₂; perfluorobutylpentane, F₄H₅; perfluorobutylhexane, F₄H₆, perfluorobutyloctane, F₄H₈; perfluorohexylethane, F₆H₂; perfluorohexylhexane, F₆H₆; and perfluorohexyloctane, F₆H₈) are experimentally determined over a wide temperature range (276–350 K). The corresponding surface thermodynamic properties and the critical temperatures of the studied compounds are estimated from the temperature dependence of the surface tension. Experimental density and vapour pressure data are employed to parameterize a generic heteronuclear coarse-grained intermolecular potential of the SAFT-γ family for PFAAs. The resulting force field is used in direct molecular-dynamics simulations to predict the experimental tensions with quantitative agreement and to explore the conformations of the molecules in the interfacial region revealing a preferential alignment of the PFAA molecules towards the interface and an enrichment of the perfluoro groups at the outer interface region.