Interpretation of the mass distribution of ejected (CsI)nCs+ ion clusters by the non-cascade sputtering model

Large (CsI)_nCs⁺ cluster ions ejected by keV ion bombardment of CsI surfaces have been observed by various researchers, notably those from the Naval Research Laboratory and the University of Manitoba. We use the non-cascade sputtering model to describe the mass distribution of these cluster ions. Reasonable agreement between theoretical predictions and experimental observations is obtained. The energy deposited by the bombarding ion giving rise to the ejection process is shown to vary with the stopping powers of the bombarding ion species. the model is also shown to be applicable to cluster ions ejected from other alkali halides.     

Secondary ion mass spectra of alkali halides

Mass spectra of positive and negative secondary ions from various alkali halides have been measured in the Manitoba time-of-flight mass spectrometer. The ions were produced by Cs⁺ and K⁺ bombardment at primary ion energies of 3 to 19 keV for the positive spectra, and 11 to 28 keV for the negative spectra. The ions measured were those emitted within a time interval ～ 20 ns after the primary ion impact. The secondary ion yields are strongly dependent on the sample composition and treatment; prior irradiation may change the yield by an order of magnitude or more. The secondary ion yields also depend strongly on the energy loss of the primary ion, but the ratio of yields of different cluster ions from a given target is almost independent of this parameter. The results appear to be consistent with models in which the clusters are ejected directly from the target, but do not determine whether or not they possess the original surface structure. The results may also be described by a recombination model if the recombination is essentially complete.     

Vibrational fluorescence of CN− centers in KCl by electronic excitation of neighbouring Tl+ centers

Abstract

Infrared emission from higher vibrational states of CN^? in KCl has been achieved by optically exciting nearby Tl⁺ ions with an excimer laser. The electronic vibrational energy transfer, already known from F_H(CN^?) in alkali halides, leads to population of vibrational states up to at least the tenth level.     

Semiempirical pseudopotential surfaces for chemical reactions: The (AB)+ X - dialkali halide systems

A generalization of the Roach-Child semiempirical pseudopotential calculation for K + NaCl to several analogous dialkali halide systems has been used to elucidate the chemical interactions governing the reaction dynamics. The Li + LiF ground-state potential surface, which exhibits a ～ 20 kcal/mole basin for isosceles Li₂F, is qualitatively similar to one obtained in a recent configurational interaction calculation. It is shown that regions of the Na₂Cl ground-state surface corresponding to Na₂ ⁺ interacting with Cl^- can be described in terms of an ion-pair Rittner potential model similar to that employed for the alkali halides. Chemical trends in the triangular complex well depths satisfactorily account for the experimentally observed transition between the collision complex mechanism (Rb + KCl) and the osculating complex model (Li + KBr) for the alkali-alkali halide exchange reactions at thermal energies. For collinear configurations with the alkalis on opposite ends, avoided intersections between the lowest two potential surfaces are characterized in terms of diabatic surfaces computed from truncated basis sets. Crossings of these surfaces account for the vibrational-electronic energy transfer between alkali atoms and vibrationally excited alkali halides. The ionic X ^- + A ₂ ⁺ potential surfaces are used to predict the product electronic excitation and partitioning of exoergicity in reactions of halogen atoms with alkali dimer molecules.     

Electronic polarisabilities of ions in alkali halide crystals

Tessman, Kahn and Shockley calculated the electronic polarisabilities of ions in alkali halide crystals using the long wavelength limiting values of the visible light dielectric constants. We have recalculated these widely used polarisabilities using the more accurate room-temperature dielectric constant data of Lowndes and Martin and a better minimisation procedure of Pirenne and Kartheuser. We have also calculated for the first time the low temperature values of these polarisabilities. The computed values of the polarisability in ų are Li⁺ 0·029, Na⁺ 0·285, K⁺ 1·149, Rb⁺ 1·707, Cs⁺ 2·789, F^? 0·876, Cl^? 3·005, Br^? 4·168, I^? 6·294 at 300°K and Li⁺ 0·029, Na⁺ 0·290, K⁺ 1·133, Rb⁺ 1·679, Cs⁺ 2·743, F^? 0·858, Cl^? 2·947, Br^? 4·091, I^? 6·116 at 4°K. The relative standard deviations for all the alkali halides are 1·20 and 1·43 per cent at 300°K and 4°K respectively justifying the additive nature of the individual ion polarisabilities.     

Ionic compressibilities and ionic radii - systematic trends

Ionic radii and compressibilities have been calculated for a number of monovalent and divalent ions and radicals on the basis of the compressible ion theory. In this theory, the compression energy of an ion is given as a two-parameter function of its radius,A exp (−r/p), the radius and compressibility of the ion being monotonically decreasing functions of the compressing force acting on it. Choosing a standard force reflecting the average environment in the alkali halides, univalent radii and compressibilities have been calculated. This is the first theory to estimate ionic compressibilities. The values show systematic trends among groups of related ions. Anions are found to be significantly more compressible than cations (e.g., the compressibilities of Ca⁺⁺, K⁺, Cl⁻ and S^{− −} are respectively 0.8530, 1.342, 2.952 and 5.150 × 10⁻¹² cm²/ dyne). Multivalent or ‘crystal’ radii and compressibilities have also been calculated by scaling the standard force by the square of the ionic charge. The calculated ionic radii are closer to experimental values than the classical empirical radii.     

Electron and photon stimulated desorption of positive ions from alkali halide surfaces

We have observed desorption of positive ions from alkali halides stimulated by low energy electron and photon bombardment. Our experiments include the first measurements of electron stimulated desorption (ESD) of Na⁺ from NaCl and the first measurements of photon stimulated desorption (PSD) of positive ions from NaCl and LiF. The energy dependence data indicate that the initial onset for Na⁺ ejection by ESD occurs at the excitation threshold of the Cl(3s) core level. Similarly for the PSD of positive ions from NaCl and LiF we can relate incident photon beam energy dependent ion yields with the production of substrate core holes. The data provide insight into the mode of initial energy transfer to the solid which leads to desorption. ESD and PSD ion yields were measured to be on the order of 10^?7 ions per incident electron or photon.     

Atomic excitations in sputtering studied with the use of composite targets

Atomic excitation phenomena in sputtering have been studied with the following combinations of projectile and target. (i) Be, B, Mg, Al, and Si bombarded with 80 keV Ar⁺ at UHV as well as with the target chamber backfilled with oxygen. (ii) Mg bombarded with 80 keV O⁺, F⁺, Ne⁺, Na⁺ Cl⁺, and Ar⁺. (iii) MgO, MgF₂, MgCl₂, MgSO₄, and several alkali halides bombarded with 80 keV Ar⁺ at UHV. Results are discussed. It is concluded that the excited-state formation takes place as electron tunneling at a fairly large separation between the target surface and the particle being sputtered. It is suggested with composite targets containing a metal element that excitation takes place predominantly at locations of the target surface where the work function is low, due to a thin, metallic surface layer, and that production of ground-state, positive secondary ions mainly takes place at target surface regions with high work function. For semiconductors, the changes caused by presence of oxygen are related to the change of the bonds in the solid from being of covalent nature to being fractionally ionic.     

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.     

Compound synthesis in TiO2 implanted with Rubidium

Rubidium ions, with energy in the range 0.1 MeV, 2.0 MeV have been implanted in TiO₂ single crystals at RT and LNT.

Defects induced by implantation have been studied by optical spectroscopy, X-ray diffraction, RBS, TEM and electrical conductivity.

During implantation, the implanted samples are blue colored after irradiation. This coloration is due to an optical absorption band localized at 900 nm which corresponds to optical transition of intrinsic defects identified as Ti³⁺. These defects are induced by a chemical reaction between the implanted ions and the oxygen of the lattice as in the case of D⁺, H⁺, Li⁺, Na⁺ and K⁺ implanted in rutile.^1-3

The synthesis of a new phase in heavily implanted rutile is exhibited by using a thermal treatment and by combining techniques such as RBS, TEM and X-ray diffraction at glancing angle in the temperature range 300°C-700°C.

This compound does not correspond to metallic precipitates of rubidium which are observed in MgO implanted with Rb ions.

Planar defects have been observed in the implanted area. A correlation is exhibited between these defects and the precipitates of the new phase. From X-ray diffraction measurements and TEM observations, the composition of the synthetized compound is likely Rb₂TiO₃.     

Heat of formation of solid solution of alkali halides

Based on a semicontinuum model, the electrostatic, the polarisation, and the repulsive energy change of a lattice is calculated numerically, as a function of the relaxation of the nearest neighbouring ions of a substitutional impurity in an alkali halide crystal. It is found that for a particular displacement, the total energy change of the lattice is a minimum. Thus the heat of formation of a dilute solid solution is obtained. Here, we report calculations on the heat of formation of the following systems-Na⁺ in LiCl, Li⁺ in NaCl, K⁺ in NaCl, Na⁺ in KCl, Rb⁺ in NaCl, Na⁺ in RbCl, F^? in NaCl, Cl^? in NaF. Br^? in NaCl and Cl^? in NaBr.     

Farbzentren in Ammoniumhalogeniden

Color centers produced by X-rays in ammonium halides at various temperatures between 20°K and room temperature have been investigated by means of paramagnetic resonance and by optical methods. Two kinds of paramagnetic defects were found to be predominant, the self-trapped hole (V _K-center) and another electron deficiency center involving a NH₃ ⁺-radical. The electronic structure of theV _K-center is the same as in the alkali halides, except that the orientation of the molecular axis is along [100] instead of [110]. The kinetics of the thermally activated motion of theV _K-centers and of their recombination with electrons has been studied. The electronic structure of the second center was derived from the hyperfine spectrum of the paramagnetic resonance. The rotation of the NH₃ ⁺ ion and its connection with the order-disorder transition in NH₄Cl has been studied.     

Etude par R.P.E. d'electrolytes vitreux appartenant au systeme B2O3-Li2O-LiCl

An EPR study of fast Li⁺ ion vitreous conductors belonging to the B₂O₃-Li₂O-LiCl system has been carried out. The samples have been subjected to X-ray irradiation at room temperature. Two types of paramagnetic centers have been observed. The first one is the Cl₂^- species (Vk center) present in the part of the vitreous domain which corresponds to low LiCl concentrations, it vanishes when Li⁺ and Cl^- begin to order. The second one is of the B.O.H.C. type often present in alkali borate glasses. Its presence shows the similarity between the boron-oxygen network of the alkali borate glasses and of our samples containing alkali chloride.     

Electronic Emission from Hg-Atoms and HgCl-Radicals Due to Collisions of Nitrogen Ions and HgCl2/Hg2Cl2 Molecules

Emission spectra of the (B-X), (C-X) and (D-X) band systems of HgCl-radical and mercury atomic lines from highly excited levels to various lower levels have been observed during collisions of N⁺ and N⁺ ₂ ions and HgCl₂/Hg₂Cl₂ molecules at different laboratory kinetic energies of the projectile ions. Emission cross-sections of the most intense mercury atomic lines and the (C-X) band system of the HgCl-radicals, have been measured in the laboratory kinetic energy range of 100–900 eV.     

Structure and thermodynamic properties of positive and negative cluster ions in saturated vapour over barium dichloride

Geometrical structure, vibration spectra, and enthalpies of dissociation have been investigated for the ions BaCl₃^?, Ba₂Cl₃⁺, Ba₃Cl₅⁺, and Ba₄Cl₇⁺ which were detected earlier in the saturated vapour over BaCl₂. Quantum chemical methods of density functional theory, the second and the fourth order Møller–Plesset perturbation theory have been applied. The effective core potential with cc-pVTZ basis set for barium atom and two full-electron basis sets including the diffuse and polarised basis functions for chlorine atom were used. The effect of the basis set size and the computation method on the results was analysed. According to the results, all the ions possess the compact shaped structure. The equilibrium geometrical structures were found as follows: the planar D_3h for BaCl₃^?, triple bridged bipyramidal D_3h for Ba₂Cl₃⁺, hexabridged D_3h for Ba₃Cl₅⁺, and septuple bridged C_2v for Ba₄Cl₇⁺. For positive ions, the different isomeric structures were considered, but no isomers for these ions have been found. The geometrical parameters and vibration frequencies were utilised for computing of thermodynamic functions of the ions, and then the thermodynamic functions were used for the treatment of the experimental mass spectrometric data. The enthalpies of formation Δ_fH°(0 K) of the ions were determined (in kJ/mol): ?994 ± 6 (BaCl₃^?), ?481 ± 10 (Ba₂Cl₃⁺), ?1276 ± 14 (Ba₃Cl₅⁺), ?2048 ± 35 (Ba₄Cl₇⁺).     

Effects of alkali metal ions on upconversion photoluminescence intensity of Er3+-doped Y2O3 nanocrystals

We investigate upconversion emissions in alkali metal ions (Li⁺, Na⁺, and K⁺) and Er³⁺-codoped Y₂O₃ nanocrystals. By introducing Li⁺, upconversion intensity is significantly enhanced, while Na⁺ and K⁺ hardly have this influence. FT-IR data give evidence that the main mechanisms of the enhanced upconversion emission cannot be attributed to the decreased surface defects. EXAFS data and variations of enhanced upconversion intensities in different samples indicate that Li⁺ can occupy the interstitial sites in lattice and thus arouse large site asymmetry. In addition, locations in the samples and effects on the upconversion emission of Na⁺ and K⁺ are discussed.     

The reactions of Cl+ (3P) and Cl+ (1D) with hydrogen sulphide. A G2 molecular orbital study

G2 ab initio molecular orbital calculations have been performed to study the potential energy surfaces (PESs) associated with the reactions of Cl⁺ in its ³P ground state and in its ¹D first excited state with hydrogen sulphide. [H₂, Cl, S]⁺ singlet and triplet state cations present very different bonding characteristics. The latter are systematically ion-dipole or hydrogen-bonded weakly bound species, while the former are covalent molecular ions. As a consequence, although the Cl⁺(³P) is 34.5 kcal mol^?1 more stable than Cl⁺(¹D), the global minimum of the singlet PES lies 37.3 kcal mol^?1 below the global minimum of the triplet PES. Both singlet and triplet potential energy surfaces show significant differences with respect to those associated with Cl⁺ + H₂O reactions as well as with SH₂ reactions with F⁺. In both cases, the major product should be SH⁺ ₂; SH⁺ and HCl⁺ being the minor products, in agreement with the experimental evidence. The estimated heat of formation for the most stable H₂SCl⁺ singlet state species is 198 ± 1 kcal mol^?1.     

Energy and angular distributions for scattering of K+ from W(110) at normal incidence

Using a K⁺ ion beam and a K neutral beam at normal incidence on a W(110) surface, we have measured the angle and energy distributions of scattered K⁺ ions at different azimuthal angles. The primary energy is in the range 12–100 eV. The measured distributions show a complex peak structure. The peaks can be assigned to different scattering mechanisms, giving rise to various rainbow phenomena.     

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.     

Thermally stimulated depolarization of Eu2+-cation vacancy dipoles in alkali halide single crystals

Ionic thermocurrent (ITC) measurements have been performed on eight alkali halide single crystals doped with divalent europium. In all cases, the observed ITC peaks were fitted with a mono-energetic model without to appeal to any dipole-dipole interaction. Values for the reorientation parameters have been calculated. The relationship T_M1nτ^?1 α E previously found for I–V complexes in alkali halides has been found to be very well obeyed for the experimental data obtained in this investigation. It is also reported that the logarithm of the experimentally determined energies for free dipole reorientation shows a linear dependence on the interaction distance between the Eu²⁺ ion and the surrounding halogen ions in the distorted cubic site occupied by this impurity in the alkali halides.