KCl crystals with a silver impurity: From point defects to oriented AgCl microcrystals in a crystalline host

This paper presents the first unambiguous optically detected magnetic-resonance (ODMR) evidence that AgCl crystals embedded in the KCl lattice and retaining the host orientation are formed in KCl crystals grown with a 2–3 mol % silver impurity. ODMR spectra were obtained of self-trapped holes, shallow electronic centers, and self-trapped excitons, which are typical of AgCl, and a number of substantially different ODMR spectra were also obtained. The differences between the ODMR spectra observed in samples cleaved from different parts of a KCl: AgCl crystal are probably accounted for by embedded AgCl crystals varying in size from large micro-to nanocrystals.     

Thermoluminescence in Ag(Cl,I) mixed crystals

The distribution of traps in AgCl + 1% mol AgI mixed crystals was obtained by thermoluminescent fractional glow technique. The distribution reveals a prominent maximum at 240 meV. These traps are characteristic of mixed crystals. Shallow traps also exist, but they appear to be connected with host AgCl crystal. The nature of the deep trap in mixed Ag(Cl, I) crystals is discussed on the basis of the fundamental optical properties of pure AgI and AgCl crystals.     

Free energies of ionic nanoclusters. Solid and coexistent solid-liquid states

A strategy to overcome some specific problems associated to the computation of free energies in clusters is presented. Free energies and entropies of solid KCl nanoclusters are determined by thermodynamic integration, and Watanabe and Reinhardt’s dynamical method, based on molecular dynamics simulations. The values are in good agreement with experimental data. From a previous theoretical prediction of the caloric curve, T(E), for the coexistence region, an equation is derived to compute the free energies of the clusters at the solid-liquid coexistence. The results are discussed in the context of the thermodynamic stability of phase coexistent states for finite and infinite systems, yielding consistent conclusions.     

Space charge regions at silver halide surfaces: Effects of divalent impurities and halogen pressure

The model first proposed by Poeppel and Blakely to account for equilibrium space charge regions in ionic crystals is extended to include effects of mobile divalent impurities. Equations are developed that account for impurities segregating to free surfaces of crystals of the AgCl type. Numerical computations have been performed and the results indicate the variation with temperature of the potential difference across the surface space charge region. The importance of accounting for the density and energy of surface sites is demonstrated. The calculation includes effects of varying the doping level of the impurities as well as the binding energy of the impurity-vacancy complex. The effect of a chlorine atmosphere on intrinsic crystals is discussed and the variation of the chemical potential of the silver ions with Cl₂ pressure is presented.     

Adaptive clustering of a quantum solvent: the LiH+ cation in bosonic helium from stochastic calculations

Calculations of the quantum structures describing the initial solvation shells of bosonic helium atoms around a polar, ionic system like LiH⁺ are reported, together with the corresponding quantum energies. The calculations were carried out using the Diffusion Monte Carlo (DMC) approach and parametric trial functions. Its final radial and angular distributions for clusters of varying size are analysed and discussed. The solvation of this ionic dopant is shown to occur in a way which is strongly affected by the orientational induction forces between the latter molecule and the solvent atoms, indicating the onset of “snowball" structures at the location of the dopant and the clear distinction between “heliophilic" and “heliophobic" regions of microsolvation.     

Dielectric critical behaviour at a metal-insulator transition under lattice compression

We study dielectric critical behaviour around a continuous metal-insulator transition in crystalline Cesium Iodide induced by changing the lattice parameter. The ab initio calculations of band structure and various quantities related to the dielectric response are performed in the transition region, within the local density approximation of the density functional theory. These calculations allow us to establish the power-law singularities of various quantities on two sides of the transition. The exponents obtained here are mean-field like due to the approximation in which interactions and disorder are treated. The critical behaviour is discussed by applying the scaling principle to the wavevector and frequency dependent dielectric function. We further investigate the effect of dielectric anomalies on optical properties by calculating the reflectance around transition region taking the ionic contribution to the dielectric function also into account. We find that the reflectance as a function of frequency shows very different kind of behaviour on both sides of the metal-insulator transition.     

Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag²⁺ ion inside of a (AgCl₆)^4? complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra.     

Resistance of a pulsed electrical breakdown channel in ionic crystals

A technique for estimating the resistance of the electrical breakdown channel in ionic crystals is proposed. This technique is based on measuring the channel velocity in a sample when a ballast resistor is connected to the circuit of a needle anode and on using the theoretical dependence of the channel velocity on the channel conductivity. The breakdown channel resistance at a voltage of 140 kV is about 6.5 kΩ in KCl and about 6.1 kΩ in KBr. These resistances are shown to characterize a gas phase. The gas-phase resistance is found to be nonuniform along the breakdown channel. The head part ～1 mm long has the maximum resistance. This head region is concluded to contain dielectric substance clusters, which then decompose into metal and halogen ions. The cluster lifetime is ～10^?9 s.     

Fractional variant of Stokes–Einstein relation in aqueous ionic solutions under external static electric fields

Both ionic solutions under an external applied static electric field E and glassy-forming liquids under undercooled state are in non-equilibrium state.In this work,molecular dynamics(MD)simulations with three aqueous alkali ion chloride(NaCl,KCl,and RbCl)ionic solutions are performed to exploit whether the glass-forming liquid analogous fractional variant of the Stokes–Einstein relation also exists in ionic solutions under E.Our results indicate that the diffusion constant decouples from the structural relaxation time under E,and a fractional variant of the Stokes–Einstein relation is observed as well as a crossover analogous to the glass-forming liquids under cooling.The fractional variant of the Stokes–Einstein relation is attributed to the E introduced deviations from Gaussian and the nonlinear effect.     

Struktur- und Absorptionspotentiale von KCl und NaCl aus Beugungsaufnahmen im konvergenten Elektronenbündel

By improvement of an earlier published preparation method for producing thin single crystals soluble in water, it is possible to determine structure and absorption potentials of some reflections of KCl and NaCl crystals by a convergent beam diffraction technique. The structure potentials evaluated on the basis of the two-beam dynamical theory are found to depend on the thickness of the crystals used. The structure potentials corrected for relativistic, thermal and many-beam effects are compared with theoretical values. The measured (220)- and (420)-absorption potentials of NaCl are in good agreement with theoretical values. Radiation damage in KCl and NaCl crystals by electron beams is observed.     

Ionic conductivity of mixed silver halide crystals

To evaluate the effects of mixed halides on the lattice defect parameters of the silver halides, we have measured the ionic conductivity both of the entire range of mixed AgBr-AgCl single crystals, aftd also of several iodide-doped crystals. For the AgBr-AgCl system, the intrinsic conductivity at a given temperature decreases monotonically from pure AgBr to pure AgCl. The deduced Frenkel defect formation energy varies only a little from 0 to 50 mole % AgCl, and then increases rapidly with further increase in AgCl content, closely paralleling the ratio of bulk modulus to dielectric constant. The defect formation energy in these crystals hence reflects the average macroscopic properties of the solid solution. For the iodide-doped crystals, however, the results are quite different. Small amounts-of iodide cause large increases in the conductivity of AgBr andiAgCl, especially in the latter. These results suggest that the elastic strain introduced by the oversized iodide ion exerts an appreciable local effect on the Frenkel defect formation, in contrast to the crystal-averaged response found for the AgBr-AgCl solid solutions. Furthermore, the Arrhenius plots for the conductivitiei of the AgBr: I specimens show curvature which suggests a temperature-dependent pairing of the solute.     

Collective excitations in fast ion conductor superlattices

Within the framework of the electromagnetic theory, the collective modes in the superlattice system composed of superionic conductors and ionic crystals are studied. The superionic conductor is described by the hydrodynamical model in which the anion cage is immersed in the cation liquid. The behavior of the modes are analysed in terms of the coupling strength between excitations pertaining to different layers. The coupling strength is controlled by varying the slab thicknesses. An interesting behavior in which the diffusion mode transforms to the relaxation mode when the coupling strength is varied from strong to weak is obtained. Also, the effect of the coupling strength on the acoustical and optical modes are shown.     

Contributions from the indirect ionic interactions to the elastic constants in the rock-salt structure crystals

Under the harmonic approximation, the contributions from the indirect ionic interactions to the elastic constants are calculated for the alkali halide and silver halide crystals with the rock-salt structure. The coupling constants of the indirect ionic interactions are calculated by the self-consistent field treatment of the local density approximation and the spherical solid model. The calculated values of the coupling constants are large for the silver ion. The indirect ionic interaction significantly affects the elastic constants. It quantitatively explains the deviation from the Cauchy relation in alkali halide crystals. Moreover, it provides a clear account for the large values of the deviation from the Cauchy relation in AgCl and AgBr.     

Theoretical determination of the 1H NMR spectrum of ethanol

GIAO calculations of the ¹H NMR chemical shifts for ethanol at the SCF and DFT levels of theory are presented. The importance of molecular geometry and basis set is discussed. Vibrational correction to the hydroxyl proton chemical shift is also considered in calculations for the monomer of ethanol. The final theoretical results for the monomer obtained at the optimized DFT/B3LYP/6-311G(d,p) geometry with the 6-311G++ (d,p) basis set for NMR are in very good agreement with gas phase experimental data. For the liquid phase ethanol the hydrogen bonding effects are taken into account by performing calculations on various clusters of ethanol. It is shown that inaccuracy due to molecular geometry and basis set in the monomer of ethanol is magnified significantly in calculations for its clusters. In this context the structure of liquid ethanol as predicted recently by quantum cluster equilibrium (QCE) theory is discussed.     

Identification of recombination centers in wide-band-gap crystals and related nanostructures from spin-dependent tunneling afterglow

The centers involved in the spin-dependent recombination in KCl: AgCl insulator-semiconductor wide-band-gap crystal structures, bulk ZnO crystals, and quantum dots based on ZnO nanocrystals have been identified by detecting electron paramagnetic resonance from tunneling afterglow. Long tunneling after-glow has been excited by short-term UV irradiation of the sample at liquid-helium temperatures. The observed magnetic quenching of the afterglow at low temperatures results from the Boltzmann polarization of spins of recombination centers. The revealed giant increase in the afterglow intensity is induced by the reorientation of spins of these centers at electron paramagnetic resonance. A new technique for recording the spectra at a high frequency of 94 GHz has been developed and used with the aim of increasing the sensitivity and spectral resolution. This technique has made it possible to separate electron and hole centers in the KCl: AgCl structures and to demonstrate that ZnO: Al quantum dots contain two types of deep acceptors.     

Low temperature space charge polarization in alkali halide crystals

Evidence is presented to indicate the presence of linear space charge polarization in single crystals of KCl and NaCl in the temperature range between liquid nitrogen temperature and 350 K. Polarization phenomena, both dipolar and space charge, were studied by means of TSPC, ITC and by the testing of Ohm's law and the Superposition principle. The results are interpreted in terms of the formation of a linear space charge, possibly caused by the trapping of ionic charge carriers within the bulk of the material.     

Growth and X-ray studies of (NaCl)x(KCl)y−x(KBr)1−y single crystals

Ternary mixed crystals of NaCl, KCl and KBr were grown by the melt method for the first time. Densities and refractive indices of all the grown crystals were determined and also used for the estimation of the bulk composition in the crystal. Lattice parameters and thermal parameters like Debye-Waller factor, mean square amplitude of vibration, Debye temperature and Debye frequency were determined from the X-ray powder diffraction data. The observed lattice parameters showed the existence of two phases in crystals with NaCl content greater than 0.1 mole fraction. The thermal parameters show a highly non-linear composition dependence. The results are reported.     

Anisotropic surface melting in lyotropic cubic crystals

From experiments with ice or metal crystals, in the vicinity of their crystal/liquid/vapor triple points, it is known that melting of crystals starts on their surfaces and is anisotropic. It is shown here by direct observations under an optical microscope that this anisotropic surface melting phenomenon occurs also in lyotropic systems. In the case of C12EO2/water mixture, it takes place in the vicinity of the peritectic Pn3m/L3/L1 triple point. Above the peritectic triple point, where the Pn3m and L1 phases coexist in the bulk, the surface of a Pn3m-in-L1 crystal is composed of (111)-type facets surrounded by rough surfaces. The angular junction suggests that rough surfaces are wet by a L3-like layer while facets stay “dry”. This is analogous to the pre-melting at rough surfaces in solid crystals. Upon cooling below the peritectic triple point, where L3 and L1 phases coexist in the bulk, a thick layer of the L3 phase grows from the pre-melted, rough Pn3m/L1 interface. Simultaneously, facets stay dry and their radius decreases. In this tri-phasic configuration, stable in a narrow temperature range, the L3/L1 and L3/Pn3m interfaces have shapes of constant mean curvature surfaces having common borders: edges of facets.     

Microhardness studies in alkali halide mixed crystals

Microhardness measurements done in KCl, KBr and in different compositions of KCl-KBr mixed crystals show that it varies nonlinearly with composition. In order to investigate the nature of defects, several techniques such as etching, ionic conductivity and dielectric loss have been employed which showed that the mixed cristals of KCl-KBr are more defective, containing a high concentration of dislocations, low-angle grain boundaries and vacancies as compared to the end products KCl and KBr. These imperfections appear to be responsible for the nonlinear variation of microhardness in mixed crystals. The microhardness studies also revealed that the difference in size of the ions constituting the mixed system are responsible for the internal strains which in turn give rise to imperfections affecting the microhardness of mixed crystals.     

Molecular dynamic simulations and global equation of state of square-well fluids with the well-widths from λ = 1.1 to 2.1

We present the results of extensive new molecular dynamic (MD) simulations in the one-phase region for square well fluids with well widths λ?=?1.10, 1.15, 1.20, 1.25, 1.375, 1.50, 1.75, 1.90, 2.0, and 2.10. These data have been used in developing a crossover equation of state (CR EOS) for square-well fluids with well widths 1.1?≤?λ?≤?2.1. The CR EOS incorporates non-analytic scaling laws in the critical region, and in the limit of low densities yields the exact second and third virial coefficients. Also in the high-temperature region, it reproduces first-order perturbation theory results. The CR EOS was tested against our new MD simulations, and earlier MD and Monte-Carlo (MC) simulations reported by other authors as well. Excellent agreement between calculated values and simulation data for all SW fluids is observed. In combination with the density-functional theory, the CR EOS is also capable of reproducing surface tension simulations with high accuracy. Application of the CR EOS for solid–liquid equilibrium calculations in combination with the Lennard–Jones and Devonshire cell model for the solid phase, is also discussed.