Electron trapping by alkali-ion impurities in alkali halides

Evidence is presented which indicates that certain transient infrared absorptions normally observed in alkali halide crystals are due to trapping of electrons by substitutional alkali-ion impurities.     

Frequency spectrum of alkali halides with impurities distributed at random

The frequency spectrum of KI-crystals statistically doped with Br^? and Cl^? ions has been calculated in a linear approximation of the dotation. For the undisturbed lattice an amplified point-ion model was applied. The dotation generates peaks in the regular band as well as localized modes in the frequency gap. The results have been compared with absorption measurements.     

On the rotation-vibration interaction of diatomic molecular impurities in cubic crystals

Devonshire's model of the dumb-bell, subjected to a stationary potential of octahedral symmetry type is generalized to be applied to a vibrating rotor. In the framework of this model the influence of the interaction of vibration and hindered rotation is investigated for Ar:HCl.     

Split-shell molecular orbital calculations on the diatomic alkali metal molecules

Absolute g-tensor calculations for planar hydrocarbon and for non-planar phenyl substituted hydrocarbon radicals are reported. The relevant interactions determining g are discussed. Calculations are performed on the basis of a second-order perturbation expansion. The electronic wavefunctions are obtained from a simplified version of Hoffmann's extended Hückel model (SEH), where all valence electrons are taken into account explicitly. For planar systems the observed linear dependence of g on the energy of the half filled π orbital is well reproduced. A qualitative analysis of this dependence, making restrictive assumptions about the σ electrons, was given earlier by Stone. The calculations for non-planar model systems reproduce the g-factor anomalies which are observed for highly twisted phenyl substituted hydrocarbon radicals. The results show the necessity of direct π-σ mixing and are consistent with recent investigations of the proton hyperfine couplings in such systems.     

New aspects on the dielectric properties of the alkali halides with divalent impurities

Dielectric losses were measured in the following crystals NaCl+ (Mg²⁺, Co²⁺, Ni²⁺, Sr²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, Ba²⁺, Pb²⁺), KCl + (Ca²⁺, Sr²⁺, Ba²⁺, ²⁺, Pb²⁺) and KBr + (Sr²⁺, Ba²⁺) in the frequency region 5–500 kHz. It was found that when the divalent cation impurity has an electronic configuration similar to the inert gases (1) no observable deviation from simple Debye theory exists (2) the activation energy Φ increases linearly with the ionic radius of the impurity.The above observations (1) and (2) do not hold when the divalent cation impurity has d-electrons in the outer subshell.     

Modes of vibrations due to (U-center + additive cation impurities) in alkali halides

Local and resonant modes due to hydride ions in various alkali halides containing additive cation impurities have been computed by the Green function technique. Local vibrations due to U-centers in alkali halides have O_h symmetry. When one of the six nearest neighbour cations is replaced by an additive impurity, the site symmetry of the system is lowered from O_h to C_4v. The phonon Green functions matríx is analysed according to the irreducible representation of the point group symmetry pertaining to the substitutional impurity. We have considered the vibrations of the hydride ion and all its six nearest neighbours. Analytical expressions have been derived for various modes of vibrations. Using group theory the 21 × 21 matrix has been block diagonalized into various irreducible representations. The effect of mass changes and the changes in short-range force constants have been taken into account. The computed results of the localized modes have been compared with the available experimental results. Good agreement has been found. Theoretical results on resonant modes are also displayed, which will be of use in future experiments on these systems.     

Dislocation damping in alkali halides

In the amplitude independent region the dislocation damping is attributed to either phonon-drag (Granato-Lücke theory) or to the compensating charge-cloud surrounding electrically charged dislocations (Robinson-Birnbaum theory). The experimental results for the dependence of the damping on temperature, frequency and dislocation charge are compared with the two theories. Since it is found that in some cases it is necessary to include both forms of damping, a more complete theory is developed which includes both terms.

In the amplitude dependent region the dislocation damping was thought to be due to the dislocations breaking away from pinning points or breaking through the compensating charge-cloud. Using the piezoelectric defect results for electrically charged dislocation in KCl the force-displacement hysteresis loop for the moving dislocations is determined together with the force-displacement curves for dislocations assuming phonon and charge-cloud damping. These results are found to be inconsistent with the “break away” models for amplitude dependence but instead to be consistent with the restoring force due to an elliptical compensation charge cloud, with a size proportional to the square root of the dislocation charge.     

Exciton states in alkali halides

Recent experiments based on modulation spectroscopy have shown that it is possible to detect exciton levels in alkali halides up to n = 4. Therefore we worked out numerical calculations in order to predict the whole exciton series in KI and RbI. In our calculations the deep exciton levels are treated by considering the actual hole-electron interaction, whereas the effective mass approximation is used for the shallow exciton levels. The direct and exchange terms of the hole-electron interaction have been evaluated by performing three and four center integrals, the Wannier wave functions appearing in such integrals being approximated by suitable gaussian expansions of atomic orbitals.It is shown that by allowing the exciton state to extend up to 42 shells of neighbors it is possible to predict the exciton levels up to n = 2, the n = 3, 4 excitons being accounted for by the effective mass approximation. Similar computations performed for excitons in solid rare gases were found in excellent agreement with the experimental data and confirmed the reliability of our method.     

Muon radiolysis in alkali halides

In order to shed new light on the initial loss of muon spin polarization, or socalled missing fraction, which is commonly observed in non-metallic solids, we have studied muon-induced excitation in various alkali halides by measuring the luminescences associated with the radiative decay of the self-trapped excitons (STE). The result strongly suggests that the spin-exchange interaction between muonium and muon radiolysis products including STE's causes fast muon depolarization in those materials.     

Single-ion parameters for interionic potentials in alkali halides

A deformation-dipole model for the interaction between ions in alkali halides is presented which is entirely based on single-ion properties. Each ion is characterized by a set of five crystal-independent parameters. With the use of only 32 adaptable parameters for eight ions, a remarkably good fit is obtained for 96 properties of 16 crystals. The single-ion parameter model is particularly useful in calculations of substitutional impurity systems.     

The influence of the static lattice distortion on the localized modes of atomic impurities in alkali halides

We have studied the influence of static distortion on the localized modes of a Li⁺ impurity in KCl and KBr using the molecular model. For off-center equilibrium positions with the impurity on a symmetry axis of the cubic host lattice the concept of structure elements has been set up to derive the symmetry properties of the vibrating molecular region. In the frame-work of a rigid ion model with only central forces the 111-off-center position turns out to be the only possible stable off-center position. For the system KCl:Li⁺ the measured resonant modes in the region of 40 cm^–1 can only be interpreted in this model as cluster vibrations. In addition we have calculated defect induced Einstein-modes with frequencies near the upper band edge.     

Muonium centers in the alkali halides

Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined inevery alkali halide. For the rocksalt alkali halides, the HF parameter A_μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogenH _i ⁰ -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperatureMu ^I -state and a high-temperatureMu ^II -state.     

Deuteron induced damage in alkali halides

Abstract

The thermoelectric and galvanomagnetic properties in the CdxHg1_xTe solid solution samples (x = 0.12; 0.15) irradiated at 300 K by electrons (3.5 MeV; by integrated fluxes up to 1.46 × 10¹⁸e/cm²) have been investigated in a wide temperature range 4.2–300 K and in magnetic fields 0–22 kOe.

It has been discovered that the electron irradiation of Cd_xHg_1–xTe crystals leads to an increase of the Hall coefficient and a decrease of the thermo e.m.f. sign inversion temperature. The concentrations and mobilities of electron and hole have been calculated on a basis of quantitative analysis of galvanomagnetic data. It has been shown that the kinetic coefficient behavior upon irradiation is due to the Te vacancy-based type radiation defect origin.     

Defects induced melting in alkali halides

In the present paper we study the pressure dependence of melting of NaCl and CsCl crystals. A formulation has been presented for the pressure dependence of melting temperature on the basis of the vacancy model using the expression for the pressure dependence of the volume of Schottky defects from the Roy-Roy equation of state. Values of pressure derivatives of melting temperature have been calculated at elevated pressures to determine the rate of change of melting temperature with increase in pressures using the data of vacancy formation energy and effective volume of Schottky defects. The vacancy model revised in the present study takes into account the variation of bulk modulus with pressure, whereas in the Ksiazek and Gorecki model, it was treated constant. Results for pressure derivative of melting temperature are calculated for the solids under study. The melting curves have also been obtained and found to compare well with results based on molecular dynamics simulation and experimental data reported in recent literature.     

Defect parameters in the alkali halides

Abstract

Methods are available which calculate the free energies of defects in ionic systems within the quasi-harmonic approximation. The Harwell SHEOL code is used to calculate the defect enthaplies and entropies for a number of alkali halides where reliable diffusion data are known. We discuss the trends in the calculations and the comparison with experiment.     

Additivity rule for the softness parameter in alkali halides

In the present communication we report an additivity rule for the repulsive potential softness parameter in alkali halides derived from the values of overlap integrals. This rule provides a new interpretation for the repulsive interactions between different ion pairs and reduces the number of parameters. The use of additivity rule eliminates the assumption that the anion-anion, anion-cation and cation-cation softness parameters are equal. Using the new model for repulsive interactions we have calculated the cohesive energy and compressibility of sixteen alkali halides with NaCl structure. The results obtained in the present study are in better agreement with experiment than those obtained earlier with the help of a traditional approach based on the Born model.     

On the Mott-Littleton dielectric theory for alkali halides

It has been demonstrated that the Mott-Littleton theory of dielectric constant is consistent with the recent experimental data on the pressure dependence of dielectric constant of alkali halides. On the other hand, the Clausius-Mossotti and Drude models yield large deviations from the observed data.