The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

紫外激光离解四氯化钛产生的钛原子的受激喇曼散射

紫外激光(259—300nm)离解四氯化钛产生了大量钛原子,它们主要处于钛原子的基态a³F₂和亚稳态a³F_3,4上。通过近共振跃迁对处于a³F_2,3,4态上的钛原子进行泵浦,观测到一系列钛原子的受激喇曼散射和受激辐射,并对所有谱线进行了认证。钛原子的受激喇曼散射的脉宽和时间分辨谱表明,紫外激光离解四氯化钛产生钛原子的过程非常迅速,估计所需时间≤1ns。 关键词：     

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.     

低温下电子束辐照产生F2+心及其荧光发射

用自制的低温装置保持LiF晶体的温度为77K,同时用电子束辐照,产生了浓度高达10¹⁷cm^-3的F₂⁺心。并对F₂⁺心荧光发射特性进行了实验观测和理论分析。 关键词：     

Selective Stimulation of Chemical Reactions by Laser Excitation

Abstract

Among the many different applications to which lasers have been put, one of the more intriguing is their potential use in photochemistry - particularly, in inducing specific reaction pathways that are not accessible from conventional broad-band excitation. One of the first of such experiments was an attempt to use a ruby laser to carry out laser-flash photolysis of Br₂, analogous to Porter's work on I₂. Since the optical energy of the laser radiation (14,400 cm^?l) was less than the Br₂ dissociation energy, direct photodissociation was not possible; instead, excited Br₂? (³π_lu) molecules were produced, which were dissociated in subsequent collisions. The Br atoms formed in this way subsequently added to halogenated olefins such as C₄F₈ and C₄F⁷Cl.¹ The first actual laser flash-photolysis experiment, carried out in Porter's laboratory, used a Q-switched ruby laser to photodissociate dihydrophthalocyanine vapor at ca. 400°C; a multi-photon process is likely to be involved in this case.² As high-power infrared lasers became available, these were used to effect the decomposition of monia, ethyl chloride, and other molecules absorbing at 10.6 μm.^3,4 It seems clear, in retrospect, that all these reactions were essentially a laser-induced pyrolysis.     

Hole-electron mechanism of F-H pair generation in RbCl crystals with impurity electron traps

Production of F, Cl ₃ ⁻ , Ag⁰, and Tl⁰ centers in RbCl:Ag and RbCl:Tl crystals by photons having energies ranging from 5 to 10 eV has been studied at 295 and 180 K. It is shown that creation of near-impurity excitations is accompanied by formation of F centers localized in the vicinity of Ag⁺ and Tl⁺ ions. F centers are produced in direct optical generation of self-trapped excitons. In addition to the well-known mechanism of F-H pair production in nonradiative recombination of electrons with self-trapped holes, a hole-electron process has been revealed for the first time to operate in RbCl:Ag having deep electron traps. By this mechanism, F-H pairs appear in the following sequence of stages: thermally stimulated unfreezing of hopping diffusion of self-trapped holes (V _K centers), tunneling electron transfer from Ag⁰ to the approaching V _K centers, and subsequent nonradiative decay of triplet self-trapped excitons near Ag⁺ ions. Fiz. Tverd. Tela (St. Petersburg) 40, 1238–1245 (July 1998)     

External-field-induced formation of stabilized F 2 + centers in colored LiF crystals

The production of complexes, which are thermally stable at room temperature, with F ₂ ⁺ centers in radiation-colored LiF crystals by the combined action of different fields is investigated. The half-life of these laser centers produced by, specifically, hard UV radiation and a shock wave increased by almost two orders of magnitude. Fiz. Tverd. Tela (St. Petersburg) 40, 2044–2050 (November 1998)     

Pressure effect on emission spectra and crystal field for La OBr : Eu

Abstract

The emission spectra for LaOBr : Eu were measured at pressures up to 13 GPa and room temperature. The pressure dependences of levels of ⁷F_0,1,2,3,4 and ⁵D_0,1,2 are given. The crystal field parameters B^k _q were computed by fitting the experimental levels. The strength of crystal field decreases with increasing pressure. A brief discussion on the observed phenomena is presented.     

A Refinement of the Hg2F2 Structure by the Use of NMR Data

Abstract

The crystal structure of Hg₂F₂ was studied in works.^1,2 The Hg₂F₂elementary cell of the tetragonal syngony with a=3.66 Å and c=10.89 Å contains two formula units, the space-group being 14/mmm. Hg₂F₂ belongs to those types of structures which possess one non-fixed coordinate (z_F and zHg); hence, the position of the fluorine nuclei may be determined from the value of the second moment of the NMR spectrum of ¹⁹F for powder sample.³ In this case it is ostensibly important, inasmuch as determining the positions of fluorine nuclei near the heavy mercury atoms presents a difficulty for X-ray analysis.     

Optical properties of (F2 +) H centers in NaCl:OH− crystals

Abstract

In this work we present new data on the formation and destruction of the laser active (F₂ ⁺)     

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.     

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.     

Oscillator strength of the strongly “forbidden” Pb 6 p 2 3 P 0 ?6 p 2 3 P 1 transition at 1278.9 nm

The “forbidden” Pb 6p^{2 3}P ₀ ↦6 p ^{2 3}P₁ line at 1278.9 nm is measured by diode laser absorption in a resistively heated hot-pipe filled with a lead vapour and argon as buffer gas. The measurements performed at a temperature of 1170 K and a lead number density of 2.4×10 ¹⁵ cm^-3 yield the oscillator strength f _F = (4.5±1.1)×10 ^-7 which corresponds to a radiative transition probability A _F = (6.1±1.5) s^-1. Within the error bars, the result is in agreement with theoretical data published by different authors. Received 11 October 2000 and Received in final form 5 January 2001     

Kinetic studies of Kr2F1 in electron-beam excited mixtures

Different mixtures containing atomic krypton and fluorinated compounds (Kr-NF₃, Kr-SF₆) and atomic krypton, argon and fluorinated compounds (Ar-Kr-NF₃, Ar-Kr-SF₆, Ar-Kr-F₂) were excited with intense e-beam pulses. The fluorescence produced by Kr₂F¹ was studied using time resolved spectroscopic techniques. Rate constants for the production and quenching of Kr₂F¹ were deduced from the measurements. In all the mixtures used, at krypton partial pressure higher than about 100 mbar, direct production from Kr¹₂ is considered as the most important formation channel of Kr₂F¹.     

High-pressure optical studies of Y2O3:Eu3+ nanoparticles

Abstract

The fluorescence spectra of Y₂O₃:Eu³⁺ nanoparticles have been measured under the pressure of up to 78 kbar at room temperature. In this pressure range, a red-shift of 0.02(1) nm/kbar^?1 is noticed for the 0–2 line (⁵D₀→⁷F₂ transition). This shift is explained by the change of negative charge of the surrounding ligands. Compatibility between measured and calculated values for the 0–2 line position was obtained. The luminescence decay curves of the ⁵D₀→⁷F₂ transition were studied up to 78 kbar and were found to behave exponentially for all pressures studied. The fluorescence lifetime τ for the 0–2 line (⁵D₀→⁷F₂ transition) slowly decreased with pressure. The pressure effect on τ for the 0–2 line (⁵D₀→⁷F₂ transition) was explained by a model which considers the pressure effect on the line position, inter-ionic distance, ion volume and polarizability, molecular volume and polarizability, molecular refractive index and the refractive index medium n _med of the surrounding hydrostatic medium. The fluorescence lifetime calculated by the present model is in close correspondence with the experimental values.     

Electron impact single detachment on the F - ions using the heavy ion storage ring CRYRING: Cross-section determination

Electron Impact Single Detachment (EISD) of F^- has been studied using the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm, Sweden. F^- ions stored in the ring were merged with an electron beam in one of the ring sections. Neutral F atoms produced in the EISD process were detected in the zero-degree direction using a surface barrier detector. The threshold for the detachment process was found to be around 7.6 eV, thus more than twice the binding energy of F^-. The cross-sections increased smoothly up to 55 eV where it reached a maximum of 1.9×10 ^-16 cm ² . At higher energies a slow decrease of the cross-section was observed, which follows the energy dependence predicted by the Bethe-Born approximation. The experiment showed that CRYRING can be used favourably for studies of anions, and several experiments are forthcoming. Received 14 June 2000 and Received in final form 11 September 2000     

Off-axis configuration of FA(II) centres in alkali halides

Abstract

The experimental values of the off-axis angle of F_A(II) dipoles in KCl:Li⁺, RbCl:Li⁺ and KF:Li⁺ are in good agreement with those obtained from theoretical estimates of the off-centre displacements of the Li⁺ ion calculated with the shell model potentials. On this basis, one can quantitatively predict the off-axis behaviour of F_A(II) centres from the calculated off-centre positions of small impurity ions in alkali halides.     

A Way To Discover Maxwell's Equations Theoretically

The Coulomb force, established in the rest frame of a source-charge Q, when transformed to a new frame moving with a velocity V has a form F = q E + q v × B, where E = E′_∥ + γE′_⊥ and B = (1/c ²)v × E and E′ is the electric field in the rest frame of the source. The quantities E and B are then manifestly interdependent. We prove that they are determined by Maxwell's equations, so they represent the electric and magnetic fields in the new frame and the force F is the well known from experiments Lorentz force. In this way Maxwell's equations may be discovered theoretically for this particular situation of uniformly moving sources. The general solutions of the discovered Maxwell's equations lead us to fields produced by accelerating sources.     

Spin–Orbit Splitting Difference and Stokes Shift in Cerium3+-Activated Aluminate Phosphors

ABSTRACT

Here we discuss the spin–orbit splitting difference in the ²F_7/2 and ²F_5/2 ground state of Ce³⁺-activated XMg₂Al₁₆O₂₇(X?Ba, Sr) phosphors. Recently we reported the optical properties in these host materials for the SSL purpose; there was no more literature available to date on these phosphor compositions. By using Gaussian curve fit analysis, we have estimated the energy level difference in the ground state of Ce³⁺ and the corresponding Stokes shift, and we compare these with those observed in previously reported works in different families of Ce³⁺-activated oxide-based phosphors.     

A computational study of model hydrogen-, halogen-, beryllium- and magnesium-bonded complexes of aziridine derivatives

ABSTRACT

A computational study of the complexes F^?/H₂O…Z-aziridine, Z-aziridine…BeH₂/MgH₂ and F^?/H₂O…Z-aziridine…BeH₂ /MgH₂ (Z = Cl, H, Li) was undertaken in order to investigate the non-covalent interactions operative in the dimers and to assess their interplay in the trimer complexes. The halogen- and hydrogen-bonds between the O and Z atoms in F^?/H₂O…Z-aziridine are enhanced in the trimers by the Be(Mg) bond and vice versa, but the lithium bond is hardly affected. In the trimers containing F^?, the H bond is more dominant than the Be(Mg) bond, whereas the Be(Mg) bond is more dominant in the halogen- and lithium-bonded analogues. On the other hand, the Be(Mg) bond makes the major contribution to the energetic stability of all of the trimers containing H₂O.