On the possibility of a forecast for off-centre configuration of Ag+ and Cu+ in alkali halide crystals

Summary The simple cut criterion based on the accurate determination of the radii of the ions in alkali halides and previously introduced by the authors for forecasting off-centre configuration of Li⁺ and F⁻ has been extended to heavy ions (Ag⁺ and Cu⁺). It has been found that this criterion is valid for the Ag⁺ ion, whereas for Cu⁺ gives a less precise forecast because of the lack in knowledge of the effective partial charge on Cu⁺ ion. It has been evidenced that the critical value of the ratior ₊ ^* /r ₊ between impurity and host ion radius which allows off-centre configuration is dependent on the impurity ion mass. Work jointly supported by the Ministero della Pubblica Istruzione and by Consiglio Nazionale delle Ricerche, Gruppo Nazionale di Struttura della Materia.     

A model for the acceptor state in II–VI compounds

The binding energy and the spatial distribution of an acceptor in an ionic semiconductor are calculated on the Anderson model with three parameters. The result is applied to the case of Li⁺, Na⁺, Cu⁺ and Ag⁺ in II–VI semiconductors. The parameters are evaluated by the dielectric theory of a chemical bond. It is shown that Li⁺ in ZnO, CdS, and CdSe forms an acceptor state with a larger amplitude at nearest-neighbor anion sites than at an impurity site; while Cu⁺ and Ag⁺ in Zn and Cd compounds have the opposite properties. The Na⁺ ion forms an acceptor state more localized densely at the impurity site in Zn compounds and vice versa in Cd compounds.     

Electron paramagnetic resonance and thermoluminescence study of Ag ions in Li2B4O7 crystals

Electron paramagnetic resonance (EPR) is used to investigate the effects of ionizing radiation on Ag-doped lithium tetraborate (Li₂B₄O₇) crystals. Two similar, yet distinct, trapped-hole centers (Ag²⁺ ions substituting for Li⁺ ions) are produced by 60 kV x rays. One Ag²⁺ ion, labeled Center A, has no nearby defects and the other Ag²⁺ ion, labeled Center B, has a neighboring impurity which is most likely a Ag⁺ ion substituting for a Li⁺ ion. The production and thermal decay properties of the two Ag²⁺ ions are described and their g matrices and ¹⁰⁷Ag and ¹⁰⁹Ag hyperfine matrices are obtained from the EPR angular dependences. The principal values of the g matrices are similar for the two centers, but the hyperfine principal values differ significantly (Center B has smaller values than Center A). There are also differences in the directions of the principal axes for the two centers. Together, these results imply (1) that the unpaired spin is less localized for Center B and (2) that the ground-state positions of the neighboring oxygen ions are different for Centers A and B. This explains why the peaks of the Ag²⁺ charge-transfer photoluminescence bands associated with Centers A and B occur at different wavelengths (502 and 725 nm, respectively). An isochronal pulsed thermal anneal shows that these radiation-induced Ag²⁺ ions serve as the recombination site for the intense thermoluminescence peak observed near 152 °C.     

Vibrational wave packet dynamics in the silver tetramer probed by NeNePo femtosecond pump-probe spectroscopy

We present results on the ultrafast dynamics of mass-selected neutral Ag₄ clusters using NeNePo (negative ion - neutral - positive ion) femtosecond pump-probe spectroscopy. One-color pump-probe spectra of the Ag₄ ^-/Ag₄/Ag₄ ⁺ system measured at 385 nm and an internal cluster temperature of 20 K display a complex beat structure over more than 60 ps. The oscillatory structure is attributed to vibrational wave packet dynamics in an excited “dark" state of neutral Ag₄. A dominant 740 fs wave packet period as well as wave packet dephasing and rephasing are observed in the spectra. Fourier analysis of the spectra yields a group of frequencies centered around 45 cm^-1 and an anharmonicity χ _e2νχ _eχ _e of 2.65 cm^-1 for the active vibrational mode. Received 30 November 2000     

Photoinduced dissociation reactions of silver fluoride cluster ions

Photoinduced dissociation in the ultraviolet region has been investigated for Ag _nF _n-1 ⁺ cluster ions. Photodissociation spectrum of Ag₂F⁺ in the energy of 3.8–5.6 eV exhibits several sharp bands corresponding to the transition to electronically excited states. In this dissociation, only the Ag₂ ⁺ ion was observed as a fragment ion. Theoretical calculation indicates that the parent Ag₂F⁺ ion has a linear Ag-F-Ag equilibrium geometries in the ground and excited states. Since conformational changes by excitation of bending vibration are necessary for the fragmentation of an F atom, this indicates that production of Ag₂ ⁺ from Ag₂F⁺ is a result of internal conversion and following conformational changes.     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

Spectroscopic investigation of isolated silver ions in lithium chloride single crystal

The temperature dependence of the absorption and fluorescence spectra of Ag⁺ impurity centers in lithium chloride is investigated and assignments are proposed on the basis of 4d¹⁰ → 4d⁹ 4s forbidden transitions made allowed by odd crystal vibrations. The strong temperature dependence of the fluorescence lifetimes indicated that the emission process is governed by a metastable level. As in the case of Cu⁺ in on-center position in alkali-halides, the experimental results may be fairly well explained with a three level model.     

Raman scattering of KI:Ag+: Exploration of a nearly unstable defect-lattice configuration

Abstract

The Raman spectra of Ag⁺ in KI exhibit between 6K and 25K two resonant modes and quasi-elastic scattering (QES), each with a different temperature behavior. The low-temperature Raman and infrared (ir) spectral features can be described within a harmonic force-constant model, which does not however account for the dramatic temperature dependence of the experimental data. They are compatible with a population transfer from a low-temperature on-center configuration to a second elastic configuration, in which the Ag⁺ ion is displaced from the regular lattice site. The QES, which dominates the Raman spectra above 20K, may reflect different types of rotational diffusion or the presence of a third elastic configuration.     

The effect of Ag substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor that crystallizes in the simple cubic structure at room temperature. Structural transitions above and below room temperature are accompanied by step-like changes in electrical conductivity. The substitution of Ag⁺ for Cu⁺ in Cu₇PSe₆ stabilized the simple cubic structure over a wider range of temperatures than is observed for the pure compound. A disproportionate decrease in electrical conductivity accompanies modest levels of silver substitution. The prominent step in electrical conductivity associated with the low-temperature crystallographic phase transition disappears in (Ag_xCu_1−x)₇PSe₆ solid solutions for a composition parameter x=0.20, replaced by two distinct changes in the slope of conductivity below room temperature.     

Metastable fragmentation of silver bromide clusters

The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag_nBr_{n - 1} ⁺ and Ag_nBr_{n + 1} ^- and Ag₁₄Br₁₃ ⁺ is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag_nBr_{n - 1} ⁺ is no more the main series, and Ag_nBr _{n - 2, 3} ⁺ series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag₃Br₃ cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag⁺-Ag⁺ repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr)₃ and to quasi-planar cyclic structures of (AgBr)_n clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH)_n, and to cuprous halide compounds. Received 9 November 2000 and Received in final form 25 January 2001     

Optical absorption spectra of the Bi<Superscript>+</Superscript> impurity center in CsCdBr<Subscript>3</Subscript> ternary bromide

Optical absorption spectra of the Bi⁺ impurity center isomorphically substituting Cs⁺ in CsCdBr3 are recorded over a wide temperature range (from 3.2 to 300 K). An analysis of the vibrational degrees of freedom of the impurity center within the framework of the model of a single effective phonon mode yields various spectroscopic parameters of the optical transition in the Bi⁺ ion, such as the zero-phonon transition energy, Huang–Rhys parameter, and effective phonon energy. The results are used to compare the properties of the Bi⁺ center in various crystalline matrices.     

EPR study of the Ag6S3O4 compound prepared by two methods

The temperature dependence of the EPR spectra of the recently discovered Ag₆S₃O₄ phase in the Ag-O-S system prepared by two methods, the known method of co-precipitation from aqueous solution and a new method depending on the interaction of Ag₂S and Ag₂SO₄ solid reagents, has been investigated. No EPR spectra were observed at room temperature, while at liquid helium temperature a number of EPR spectra have been recorded, which disappeared upon increasing temperature up to liquid nitrogen temperature. The sample obtained by the co-precipitation method revealed an intense, rich EPR spectrum that has been tentatively interpreted assuming the presence of at least two different Ag²⁺ ion complexes, one monomer resulting in an intense anisotropic, rhombic EPR powder pattern with g₁ = 1.93(1), g₂ = 2.025(3), g₃ = 2.094(5), hyperfine constants A₁ = = A₂ = 60(5) · 10^?4 cm^?1,A ₃ = 90(5) · 10^?4 cm^?1 and one dimer EPR pattern presumably involving a pair of Ag²⁺ ions with internuclear separation of 4.3 Å. However, the presence of larger clusters could not be excluded. On the other hand, the sample obtained by a solid state reaction method has given rise to two rather weak EPR lines centered at g_eff = 2.105(3) and g_eff = 4.213(3), respectively.     

Temperature variation of the Debye-Waller factors of metal and halide ions in CsCl-Br solid solutions between room temperature and 90°K by powder X-ray diffraction

Solid solutions of CsCl-Br in different molal concentrations were prepared and X-ray diffractograms taken. The integrated intensities of the Bragg peaks have been estimated and structure factors were obtained. The crystal lattice in each of these solid solution samples is made up of a random distribution of Cs⁺, Cl^? and Br^? ions depending upon the molal concentration. A pseudo-atom model has been proposed in which the Cs⁺ ions occupy (000) position and a pseudo-atom occupies (1/2 1/2 1/2) position. The presence of incoherence scattering in these solid solutions has been considered by applying the necessary correction to the atomic scattering factors. The integrated intensities have been analysed and the temperature variation of the Debye-Waller factors of the metal (Cs⁺) ion and the pseudo ion (CB^?) have been estimated.     

Features of the absorption spectra of thin films of M 2Ag1 − x CuxI3 solid solutions (M = Rb, Cs)

The absorption spectra of thin films of (MI)_{1 ? y} (Ag_{1 ? x} Cu_xI)_y solid solutions (M = Rb, Cs) with the initial molar concentration y = 0.33 have been investigated. It is established that, at low concentrations x, a local exciton band due to Cu⁺ ions is split off from the main long-wavelength exciton bands. In Rb₂Ag_{1 ? x} Cu_xI₃ solutions, the concentration shift of exciton bands indicates the formation of a persistent-type exciton spectrum. However, in Rb₂Ag_{1 ? x} Cu_xI₃ with x ≥ 0.5 and in Cs₂Ag_{1 ? x} Cu_xI₃ with x > 0.2, exciton spectra of amalgamation type are observed, which are related to the formation of more stable M ₃Ag_{2 ? 2x} Cu_2x I₅ solid solutions. The formation of these solutions leads to broadening of the exciton bands and to the concentration transition from persistent-to amalgamation-type exciton spectra.     

Fabrication and characterization of double-diffused waveguides

An experimental study of two-step Ag⁺/Na⁺ ion exchange in BK-7 glass substrates in molten solutions consisting of AgNO₃/NaNO₃ mixtures is presented. This paper describes a method for evaluating the measured mode index spectra and the index profile of double-diffused semiburied waveguides. They are first diffused at 320°C in 2% melt and are then converted to semiburied waveguides by a second diffusion step consisting of a short-time reimmersion in a 0.25% melt.     

Formation of copper/gold solid solutions by ion beam mixing

The formation of copper/gold solid solutions due to ion beam mixing was studied by Rutherford backscattering, high-voltage electron microscopy and transmission high-energy electron diffraction. Irradiation of multilayered Cu/Au thin films were performed with Xe⁺ ions or Ar⁺ ions at room temperature to doses ranging from 5×10¹⁵ to 2.5×10¹⁶ ions/cm² and energies from 100 to 300 keV. The ion beam mixing leads to uniformly mixed metal layers. The grain size of mixed layers is pronounced increase. It was found that Cu/Au solid solutions are formed with different composition in dependence on itinial composition and implantation dose. Cu-rich and Au-rich solid solutions are induced by ion beam mixing at an initial composition Cu _x Au_100–x withx70. In addition to these solid solutions, a solid solution of middle composition Cu₆₀...₄₀Au₄₀...₆₀ is formed for an initial composition withx<70. The kinetics of formation of solid solution is discussed as a function of the initial composition and implantation dose. Post-annealing experiments of mixed Cu₅₀Au₅₀ multilayers lead to lattice transformations and provide a superlattice structure CuAuI of the L1₀-type. With this process of ordering is associated the formation of dislocation loops.     

Non-interferometric transient quantitative phase microscopy for ultrafast engineering

Lead-free piezoelectric ceramics Bi_0.5(Na_1-x-yK_xAg_y)_0.5TiO₃ [BNKAT(x/y)] have been synthesized by the mixed oxide method. The effects of the amount of K⁺ and Ag⁺ on the electrical properties were examined. X-ray diffraction patterns indicate that K⁺ and Ag⁺ ions partially substitute for the Na⁺ ions in Bi_0.5Na_0.5TiO₃ and form a solid solution during sintering. At room temperature, the ceramics exhibit good performances with piezoelectric constant d₃₃=189 pC/N, electromechanical coupling factor k_p=35.0%, remanent polarization P_r=39.5 μC/cm², and coercive field E_c=3.3 kV/mm, respectively. The curves of the dielectric constant ε_r and loss tangent tan δ versus temperature show that the transition temperature from ferroelectric to anti-ferroelectric phase decreases with increasing the K⁺ content for the compositions researched. The dependencies of k_p and polarization versus electric (P–E) hysteresis loops on temperature reveal that the depolarization temperature T_d of BNKAT(0.15/0.015) ceramics, which have good piezoelectric properties (d₃₃=134 pC/N, k_p=32.5%) and strong ferroelectricity (P_r=39.5 μC/cm², E_c=4.1 kV/mm) at room temperature, is above 160 °C. PACS 77.22.-d; 77.65.Bn; 77.80.Bh; 77.80.Dj; 77.84.Dy     

An electron spin resonance study of dimeric,trimeric, and tetrameric paramagnetic silver atom clusters

The low temperature γ-irradiation of frozen benzene solutions containing AgClO₄ leads directly to the formation of the paramagnetic species Ag₂ ⁺, no Ag⁰ centre being detected. When benzene or toluene solutions containing AgBF₄ were similarly treated and the matrix carefully annealed, well-resolved E.S.R. spectra attributed to paramagnetic clusters containing three and four equivalent silver atoms were detected. The lack of resolved anisotropy in the spectrum of the trimer and tetramer are thought to argue in favour of a triangular and tetrahedral geometry respectively rather than linear chains.     

Thermoelectric power of the vitreous electrolyte (AgI)0.79(Ag2O.B2O3)0.21

We have determined the thermoelectric power ? of the high ionic conductivity glass (AgI)_0.79(Ag₂O.B₂O₃)_0.21; ? is negative throughout the investigated T range, 320–500 K. The heat of transport of the mobile Ag⁺, Q_Ag, taken as the slope of the straight line fitting ? versus 1/T, is quite lower than the activation energy obtained from conductivity data, viz. Q_Ag = 2.81 kcal/mole^-1 < E_act = 4.34 kcalmole^-1. To circumvent this discrepancy, the analysis of the experimental data is carried out as follows: (i) it is supposed that Q_Ag = E_act in agreement with the free ion theory for solid electrolytes; (ii) the vibrational part of the silver ion entropy, S(Ag⁺, vib), is assumed to be equal to the entropy of silver, S(Ag); (iii) on the ground of a structural model for this kind of glasses, the ideal configurational entropy of the mobile Ag⁺, S(Ag⁺, conf)_id, is evaluated through a statistical approach. The ideal ionic entropy is defined as S(Ag⁺)_id = {S(Ag⁺, vib) + S(Ag⁺, conf)_id}; (iv) the difference {S(Ag⁺)_exp - S(Ag⁺)_id} is viewed as an excess entropy and is described according to the classical model of the regular solutions.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.