Manganese centers with various valency in alkali halides

Abstract

Optical absorption bands and epr spectra of NaCl: Mn⁺⁺ X-irradiated at liquid nitrogen and room temperature are studied. Manganese epr spectra are divided into three classes, based on the value of hyperfme splitting constants. It is shown that the epr spectra with the hyperhe splitting constants of around 250 × 10-⁴, 80 × 10^?4 and 20 × 10^?4 cm^?1 are caused by Mn⁺, Mn⁺⁺ and Mn⁹, respectively. Formation of several manganese centers by X-irradiation is discussed. It is suggested that optical absorption bands at 410 and 440 nm are caused by Mn^O at the lattice site and that the Mn^O center which gives an epr spectrum with A = 15. 5 × 10^?4 cm^?1 is associated with a Mn⁰ center which is not at a substitutional site.     

Dislocation spectroscopy of crystals

A new method of studying the energy characteristics of dislocations is proposed, which is based on the investigation of the interaction of moving dislocations with purposefully introduced electronic and hole centers. A study has been made of KCl, NaCl, KBr, LiF, and KI alkali halide crystals containing electronic F and hole V _K and Me ⁺⁺ (Cu⁺⁺, Ag⁺⁺, Tl⁺⁺, In⁺⁺) centers. Investigation of the temperature dependence of the dislocation interaction with the F centers permitted determination of the position of the dislocation-induced electronic band (DEB) in the band diagram of the crystal. In KCl, the DEB is separated by ≈2.2 eV from the conduction-band minimum. It is shown that dislocations transport holes from the centers lying below the dislocation-induced hole band (DHB) (X ⁺, In⁺⁺, Tl⁺⁺, V _K) to those above the DHB (the Cu⁺ and Ag⁺ centers). Such a process is temperature independent. The DHB position in the crystal band diagram has been determined; in KCl it is separated by ≈1.6 eV from the valence-band top. The effective radii of the dislocation interaction with the electronic F and hole X ⁺, V _K, and Tl⁺⁺ centers have been found. Fiz. Tverd. Tela (St. Petersburg) 41, 2139–2146 (December 1999)     

Infrared absorption of aligned H−Na+H− complexes in Kcl crystals

The localized vibrations of a complex in KCl consisting of a triangular array of two H^? ions and one Na⁺ ion in substitutional, neighboring positions have been observed in infrared absorption. As one would expect for such a molecule, five modes are observed: two longitudinal modes at 365 and 508 cm^-1, two complanar transverse modes along <110> at 459 and 562 cm^?1, and one transverse mode along <100> at 551 cm^?1.     

CU+ high doping effects in KCl and KBr films

Abstract

Highly Cu⁺ doped KCl and KBr polycrystalline films were investigated in the range of 10²⁰-10²¹ cm^?3 Cu⁺ concentration. Several techniques were used to obtain the optical and structural properties, as optical absorption and transmittance, electronic microscopy (SEM), X-ray diffraction and ellipsometry. The Cu⁺ off-center effect is still present in the films, as determined by optical and thermally stimulated depolarization current measurements (TSDC). The films were obtained by thermal evaporation, and the corresponding doping Cu-halide is introduced in the same evaporating crucible. Samples with diverse concentrations, ranging from nominal 1 to 10% mole, were prepared. The increase of Cu⁺ concentration results in an improved cyrstallynity of the grains, with higher density and a better transmittance of the film above 350 nm. Optical application as UV filter device can be considered.     

Effect of absorbing microinhomogeneities on optical damage to Alkali-Halide crystals

Micropores up to 30?C100 ??m in size (bulk density ??10⁵ cm^?3) are obtained in NaCl, KCl, KBr, and RbI via the effect of a pulse of a CO₂ laser with power density 10⁶?C10⁷ W cm^?2 up to 5 ??s long. When a pore appears, plasma formation is initiated. The average temperature is ??5500 K and the pressure is ??10⁴ kg cm^?2. The dependence of the average weight of the material removed from the pore on the energy of the crystal lattice is found. Pore formation occurs mainly via the effect of the radiation pulse, due to evaporation at the absorption wave front (velocity, 5 m s^?1) and plastic deformation. The annealing kinetics of micropores and the effect of the ionizing radiation on the bulk pore formation in NaCl crystals are investigated.     

Anionische Silberzentren („B-Zentren“) in Alkalihalogeniden

It is proposed that negatively charged silver ions on anion sites are responsible for theB bands found in silver doped alkalihalides. Experimental investigations confirming this model of theB center are presented. Optical absorption and emission ofB centers were measured in seven alkalihalides in the temperature range from 450 to 4 °K. Configuration coordinate diagrams were obtained for KCl, KBr, and KI. A chemical method was used to determine the charge of theB center. Thermal or optical excitation causes theB centers to dissociate into neutral silver atoms andF centers. The Ag⁰ centers are bound to interstitial positions at low temperature. At high temperature they collect together forming colloidal centers. TetragonalB _A centers were formed during optical bleaching of theB band in mixed crystals of the type KCl+ΔNaCl. Their absorption and emission spectra, optical orientation, and polarized emission were investigated. These properties are shown to be similar to those ofF _A centers.B _A fluorescence polarized almost completely in the [100] direction was observed. A Jahn-Teller splitting of theB absorption band was resolved in RbCl at low temperature. The splitting confirms the configuration5s² for the Ag^? ion. The results are compared with those for the isoelectronic centers In⁺ and Sn⁺⁺. Thin films of alkalihalides containing small amounts of silver, copper, or thallium were condensed simultaneously with alkali vapor. New bands in the UV region were found, possibly due to Cu^? and Tl^? centers.     

Temperature Effect on the IR Absorption Spectra of Hydrogen Bonded (N[sbnd]…N)+ Homoconjugated Cations

Abstract

The effect of temperature on the absorption spectra from 50 to 3200 cm^?1 of a number of amine semiperchlorates and perchlorates of amines with two basic centres in which the hydrogen bridges (N [sbnd] H…N)⁺ are formed, was investigated. Three broad absorption regions may be distinguished in the spectrum, viz., between 100 and 900 cm^?1, 600 and 1800 cm^?1 and 1700 and 2900 cm^?1. The latter one may be assigned to the stretching vibration ν_S (N [sbnd] H…N).

A shift of this band peak (which is usually a doublet at room temperature for aromatic amines) towards longer wavelengths on decreasing the temperature may be an evidence that the bridge becomes shorter. Simultaneously with these changes, most salts under investigation exhibit a strong increase in low-frequency absorption intensity at about 400–600 cm^?1. It may be suggested that this absorption results from a transition between the split levels of the zero vibrational state.     

Some CNDO Calculations and Structural Spectroscopic Studies of Paracetamol Complexes

Through complete neglect of differential overlap (CNDO) calculations of the electronic energy among different possible structures of paracetamol (PA) molecule, it has been concluded that its structure has C_s point group symmetry of the cis‐form in which the methyl group has a restricted free rotation around its bond with the carbon atom of the amide group. The electronic spectra of PA compound were studied in different polar and nonpolar solvents. The temperature effect on the electronic spectra confirms the presence of one conformer only. The hydrogen bonding and the orientation energies of the polar solvents were determined from the studies of mixed solvents. Complexes of PA with metal ions M(II) (Cu⁺⁺, Zn⁺⁺, or Fe⁺⁺) of ratio 2:1, respectively, were prepared, and their structure has been confirmed by elemental analysis, atomic absorption spectra, IR spectra, and ¹H‐NMR spectra. It has been concluded that the structure of the complexes has C_2h point group symmetry in which two PA molecules are chelated to any one of the metal ions Cu⁺⁺, Zn⁺⁺, and Fe⁺⁺.     

Electron-lattice interaction of Ag− and Cu− centers in alkali halides

Absorption, emission, and excitation spectra of Ag^? centers in KCl, RbCl, CsCl, and CsBr are measured at low temperatures. The positions of theA emission bands are slightly different afterC andA band excitation, respectively. This is believed to be due to the existence of two different types of minima in the adiabatic potential energy surface of the³ T _1u state. The symmetry of the energy minima in the¹ T _1u state is trigonal for KCl∶Ag^? and Cu^?, but tetragonal for CsBr∶Ag^?. This becomes evident from the polarization properties of the emission. The energy and temperature dependence of the polarization is discussed. Uniaxial stress causes polarized emission of Ag^? and Cu^? centers measured from LHeT to 100 K. This is due to a splitting and mixing of the relaxed excited states by the stress. The effects are used to calculate the coupling constants between thep electron and theE _g andT _2g lattice modes. They are compared with predictions from the point-charge model for different lattice structures. A new assignment of the absorption bands of KCl∶Cu^? to the excited states of Cu^? is established on measurements of emission spectra and lifetimes.     

Optical properties of Cu+ centers in NaCl

Different aggregation-precipitation states of Cu⁺ have been characterized by absorption bands peaked at 305, 350 and 372–383 nm.The absorption bands at 372–383 nm, observed exclusively in the most doped crystal, have been associated with the Z₁₂, Z₃ excitons of CuCl microcrystals incorporated into the NaCl matrix Their positions shift to low energies with increasing concentration, as expected for a decrease in the stress over the precipitate.The Z1₁₂, Z₃ exciton bands of CuCl microcrystals precipitated in NaCl can be observed by the optical absorption spectrum without reaching saturation Therefore, this technique could be an alternative method to studies of CuCl thin-film depositions or reflectivity of CuCl single crystals.The red emission band observed at 600 nm is a long-lived emission (τ? 29 ms) at variance with the behavior reported for the Cu⁺ emission It is related to energy transfer processes from Cu⁺ to Mn²⁺.     

Absorption coefficient of infrared laser window materials

The absorption coefficient of a number of potential i.r. laser window materials has been measured in the region of multiphonon absorption. Absorptions as low as 0·004 cm^?1 have been detected by using thick samples and a differential technique with a dual-beam spectrophotometer. The absorption coefficients of LiF, CaF₂, BaF₂, SrF₂, MgF₂, Al₂O₃, KCl, NaCl and KBr all decrease exponentially with increasing wavenumber. The slope of the exponential bears a nearly constant relationship to the longitudinal optical phonon frequency, consistent with a multiphonon process whose strength depends on the number of phonons generated. Absorption data are also presented for Si, Ge, GaAs: Cr, GaAs: Fe, ZnSe and CdTe.     

Anti-stokes emission in an additively colored KCl caused by excitation with a Nd: YAG laser

Abstract

We have observed the quadratic laser power dependence of two anti-Stokes emission bands at 15100cm^?1 and 14000cm^?1 in an additively colored KCl when excited with a Nd:YAG laser. The cross section of two photon absorption to cause the 14000cm^?1 band is estimated to be 4×10^?40cm⁴sec. We have observed that emission intensities are dependent on temperature in the range between 4. 2K and 130K. They are enhanced by means of optical bleaching and also with the increase of the F concentration. From a qualitative analysis of these observations, we propose that these emissions are correlated to the loose aggregation of the F centers.     

RAMAN STUDY ON (Pb) CENTERS IN SINGLE CRYSTALS OF ALKALI HALIDES DOPED WITH LEAD

Low frequency modes were observed in a series of alkali halides doped with lead after X-irradiation at 77K. The peak positions of the Raman signals are at 34cm^-1 for NaCl:Pb²⁺, 30cm^-1 for KCl:Pb²⁺,28cm^-1 for RbCl:Pb²⁺ and 22cm^-1 for KBr:Pb²⁺. They are assigned to the inelastic light scattering caused by the local vibration of X^-_i (Pb⁺) center, which consists of an interstitial halogen ion stabilized by a substitutional ion Pb⁺ . Polarized Raman measurements and Behavior Typer(BT) analysis show that the symmetry of the X^-_i (Pb⁺) center belongs to the point group C_3v A structure model of the X^-_i (Pb⁺) center is proposed based on the Raman data and the result of BT analysis.     

Diffusion of heterovalent ions in ionic crystals

Diffusion of divalent and trivalent cations is investigated in NaCl and KCl under conditions of heterodiffusion at infinite dilution. This purpose is achieved by letting radiotracers of very strong specific activity diffuse in the intrinsic range of highly pure single crystals. The importance of the experimental procedures in yielding reliable results is emphasized. Thus, Co⁺⁺, although supposedly characterized by an anomalous diffusion in NaCl and KCl, gives very good diffusion profiles with the carrier-free isotope Co-58. Also Fe⁺⁺⁺, whose diffusion was considered impossible, gives good diffusion profiles with certain experimental precautions. Analysis of the data gives, for the diffusion of Co⁺⁺, the migration enthalpy of 0.76 eV in NaCl and 0.66 eV in KCl and the migration entropy of −2.84 k in NaCl and −1.45 k in KCl. These results are in good agreement with the values for the full set of divalent cations.     

Optical absorption due to paraexciton of Cu2O

In Cu₂O a new absorption line is observed at 97 cm^?1 below the n =1 of the yellow exciton (triply degenerate orthoexciton) under a strong magnetic field at 4.2 K. The line is assigned as a transition to a nondegenerate spin triplet state Γ⁺₂ (paraexciton). An analysis including the effects due to the n =1 of the green exciton yields 364 cm^?1 as the exchange energy, and 2.68 and ?1.02, or 1.02 and ?2.68 as the g-factors of the conduction and valence bands forming the yellow exciton.     

Optical study in a novel quaternary ionic crystal doped with europium

In this Letter, the novel quaternary alkali halide crystal KCl:KBr:RbCl:RbBr doped with europium, each component in a 25% molar fraction and 0.5% of Eu⁺⁺, is reported. The value of its refractive index was measured, the crystallographic properties are characterized by X-ray diffractometry, the optical properties were studied by optical absorption in UV-VIS region, and by photoluminescence under N₂ laser excitation at 12 K and at RT. The diffractometer diagram of a powder sample shows a single phase and a well defined value of the lattice constant. From the optical absorption spectra of europium, the value of 10 Dq parameter is obtained, the result is in good agreement with X-rays analysis. It was also observed that decay times of the blue emission is independent of temperature and only one decay component is present in the quenched samples. From obtained data, it is suggested that the symmetry of the Eu⁺⁺ site in the quaternary crystal KCl_0.25KBr_0.25RbCl_0.25RbBr_0.25 is similar to a quenched sample of a single component crystal.     

Experimental study of the reaction vp → μ−pπ+: Gargamelle neutrino propane experiment

A sample of 357 events fitting the reaction ν + p → μ^? + p + π⁺ on free proton is obtained from the Gargamelle neutrino propane experiment at the CERN-PS. The average value of the cross section above 1 GeV is found to be (0.60 ± 0.07) 10^?38 cm². The reaction is dominated by the production of the Δ⁺⁺(1232) resonance. Results on the Δ⁺⁺ spin density matrix are given.     

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.     

ESR and optical study of Cu2+-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II)

ESR studies were conducted on Cu²⁺-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II). Two Cu²⁺ lattice sites, Cu²⁺(I) and Cu²⁺(II), were identified. These sites exhibit two sets of four hyperfine lines in all directions. The g factor and hyperfine splitting were calculated from ESR absorption spectra: g_x ?=?2.0201?±?0.002, g_y ?=?2.0900?±?0.002, g_z ?=?2.1634?±?0.002, A_x ?=?(30?±?2)?×?10^?4?cm^?1, A_y ?=?(40?±?2)?×?10^?4?cm^?1 and A_z ?=?(154?±?2)?×?10^?4?cm^?1. It was found that Cu²⁺ enters the lattice substitutionally. The ground-state wavefunction of the Cu²⁺ ion in this lattice was determined from the spin Hamiltonian constants obtained from the ESR studies. With the help of an optical absorption study, the nature of the bonding in the complex is also discussed.     

Electron-lattice interaction in the absorption spectra of thallium doped alkali halides

The electron-lattice interaction of NaCl:Tl⁺, KCl:Tl⁺, KBr:Tl⁺, and KI:Tl⁺ is discussed using the moments of the absorption bands. The discussion is based on a theory ofToyozawa andInoue andHonma. Consistency of the data is found for the absorption measurements. An analysis of the band shift under applied stress shows for theA-band in KCl and KBr and for theA- andB-band in KI that the electronlattice coupling constants derived from these data assuming next neighbour interaction differ considerably from those derived from the second moments of the bands.