Transport processes in NaCl single crystals doped with a trivalent cation; solubility,association and migration of Y3+

The self-diffusion coefficient of ²²Na⁺ and the ionic conductivity are measured as a function of temperature in NaCl single crystals doped with labelled yttrium ions, as well as the diffusion coefficient of ⁸⁸Y³⁺. We give the theoretical equations for the transport processes in the alkali halides doped with a trivalent cation; These are derived from the theory of the crystals doped with divalent cations. Solubility of YCl₃ in NaCl is accurately determined through a radioactive technique. The free enthalpy of solubility of free Y³⁺ is: (2.91?13 kT) eV. A good fit of the whole set of data is obtained by treating the association between Y³⁺ ions and vacancies by the single equation $\text{K}{}_2\text{= 12}\text{exp}\text{(-9.5)}\text{exp}\text{(}\text{1.17}\text{kT}\text{)}$. The jump frequency of Y³⁺ is $\text{w}{}_2\text{= 1.37 × 10}{}^{13}\text{exp}\text{(-}\text{0.98}\text{kT}\text{)}\text{sec}{}^{-1}$. The results are compared to those characterising the divalent foreign cations.     

The electronic Raman spectrum of cobalt doped MgO

The energies of the ⁴T_1g states of Co²⁺ as a dilute substitutional impurity in MgO relative to the ground Λ_6g doublet have been found by low temperature Raman spectroscopy to be two Λ_8g states at 305 ± 3 cm^?1 and 930 ± 3 cm^?1; the remaining Λ_7g energy is predicted to be in the 980–1010 cm^?1 range the corresponding Λ_6g → Λ_7g Raman transition being weak and buried in the extensive two-phonon background. A second-order perturbation calculation which couples the spin-orbit states to both E_g and T_2g modes of vibration gives a weak but important Jahn-Teller stabilization energy for the Λ_8g states.     

X-ray photoelectron diffraction from adsorbate core levels in the energy range 500–10000 ev and with polarized radiation: a theoretical study

X-ray photoelectron diffraction (XPD) from adsorbate core levels shows considerable promise as a surface-structural probe, especially since a simple single-scattering theory appears capable of describing such photoelectron diffraction. In the past, several types of XPD structural investigations have been made using conventional Al Kα radiation, including determinations of bond orientations for diatomic molecular adsorption and of vertical bond distances for atomic adsorption. In this work, a theoretical investigation has been made within the single-scattering cluster model to determine the possible advantages and disadvantages of using different photon energies over a broad range from 500 to 10000 eV and/or a polarized radiation source in such structure determinations. Two test cases, of intramolecular scattering in C 1s polar scans above vertically adsorbed CO and of interatomic scattering in O 1s azimuthal scans for c (2 × 2) O on Cu(100), are considered in detail. In general, precision in determining bond orientations can be unproved by using higher energies and/or polarized radiation, although it may be more difficult to obtain the data owing to lower percent effects and lower total intensities. In azimuthal scans, going to higher energy yields narrower features, but requires much lower takeoff angles and concomitantly lower intensities. Other aspects of using variable energy and polarization in XPD are also considered.     

Disappearance of the heat capacity peak of Sc3In around the curie temperature in high magnetic fields

The low temperature (1.3–20.0 K) heat capacity of the weak itinerant electron ferromagnet Sc₃In was measured in magnetic fields up to ～ 10 T. The heat capacity peak observed around T_c = 6.0 K in zero field becomes smaller with increasing fields and at 9.98 T its magnetic entropy is ≈ 18% of the zero field value. Above T_c, the spin fluctuation contribution to the heat capacity, which is enhanced by the magnetic field at lower fields (?5 T), is quenched at higher fields (?5 T). This depression of the spin fluctuation contibution to the heat capacity by the high magnetic fields occurs at lower magnetic fields than had been considered possible heretofore. Our results suggest that the itinerant ferromagnetism is Sc₃In is completely quenched at 12 T.     

Raman and IR spectra of crystalline phosphine in the γ phase

The γ phase of crystalline phosphine has been studied using IR and Raman spectroscopy. The observations include both pure phases, PH₃ and PD₃, and many of the modes of PH₃, PH₂D and PHD₂ dilute in PD₃ as well as of PD₃, PD₂H and PDH₃ dilute in PH₃. The phase transition β → γ is very slow for PH₃, but much more rapid for PD₃.Evidence is adduced pointing to the existence of inequivalent sites in this crystal, but none of a number of suggested models for the unit cell is entirely consistent with the numbers of multiplet components of the internal modes, nor with the numbers of external (lattice) modes observed in the IR and Raman.     

Interpretation of auger energy shifts of silicon in solid silicon compounds

Chemical shifts of Auger transitions and photoelectron binding energies of silicon have been measured and interpreted using the quasi-atomic approach. The Si KL_2,3L_2,3 and L_2,3V₁V₁ Auger transitions and the binding energies of Si 2p and of the valence electrons at the maximum of the density of states V₁ have been investigated in solid silicon and in the compounds SiC, Si₃N₄, SiO₂, Na₂SiF₆ and T₃Si (T = V, Cr, Mn, Fe, Co, Ni). The relaxation-energy shift ΔR^ea_S(2p, 2p) describing the polarization effect (final-state effect) has been evaluated by AES and XPS measurements. Furthermore, the extra-atomic relaxation energy R^ea_D(2p) of the 2p electrons has been determined experimentally for silicon atoms in differing environments. This allows estimation of the potential parameter V(2p) describing the potential effect (initial-state effect). In general R^ea_D(2p) was found to be more sensitive to changes in chemical bonding than V2p). The behaviour of the quasi-atomic Si V₁ electrons seems to be the converse.     

An investigation of the effect of the nearest surroundings on the formation of V Lα emission bands for solid solutions of rare earth orthovanadates—orthophosphates

The V Lα, P Kβ and O Kα X-ray emission spectra for solid solutions YVO₄—YPO₄ and EuVO₄—EuPO₄ have been studied. It is shown that with an increase in concentration of orthophosphate in a substitutional solid solution a hump appears in the low energy part of the V Lα spectrum, corresponding in energy to the P Kβ spectrum. The cluster calculation of the electronic structure of solid solutions YVO₄—YPO₄, carried out by the Extended Hückel method, explains this effect as due to the hybridization of V 3d and P 3p states when [PO₄ ] complexes are introduced into the orthovanadate tetrahedral lattice.     

RF field dependence of memory echoes in LiNbO3 and GaAs powder

Measurements of the rf electric field dependence of the amplitude of the “memory” echo in LiNbO₃ and GaAs powders are reported. Consistent with the torque-rotation model, the dependence on each of the three applied rf pulses is linear in the low power regime. At high power, more complex behavior is found including an irreversible decrease in the echo amplitude when the third applied pulse is larger than the preceeding two pulses.     

Observation of helicon-excited electron paramagnetic resonance in a high-mobility semiconductor

Helicon waves can be exploited in EPR studies of localized magnetic moments in high-conductivity semiconductors when the free carriers have small effective mass and high mobility. In an electron plasma helicons have precisely the polarization required to elicit EPR, and the plasma background actually enhances the resonance intensity. Microwave transmission experiments on Hg_1-xMn_xTe, a narrow-gap semiconductor with localized Mn⁺⁺ magnetic moments, are described to illustrate this effect.     

Numerical solution of the Hodgkin-Huxley equations in a moving coordinate system. Simulation of nerve impulse transmission over long distances

The theory required for the solution of the Hodgkin-Huxley equations for the transmission of the nerve impulse in a moving coordinate system are presented. Using this theory, simulations of the transmission of the nerve impulse over large distances (e.g., 1 m) may be carried out rapidly and accurately. The above theory may be applied to other diffusion problems by appropriate modification to the problem concerned.     

Many-electron effects in the XPS spectra of Cu and Ag

The L and M XPS spectra of Cu (Z = 29) and the M and N spectra of Ag (Z = 47) are measured. The lineshift and the line-width of the L, M, and N core levels are analysed in a systematic way from the viewpoint of dynamic decay processes and fluctuations of a hole. The non-relativistic diagrammatic many-body calculations give much better agreement with the measured linewidths than the conventional methods because of a consistent treatment of correlation and localization effects.     

Study of combined electroreflectance and double layer effects at lead electrodes

Reflectance changes at lead electrodes have been measured as a function of surface charge at 45° and 70° angles of incidence using solutions of sodium fluoride and quaternary ammonium salts. These solutions were chosen so as to provide quite different composition for the inner layer at the metal/solution interface, and hence different optical contributions there from. Linear reflectance-surface charge relation has been observed for NaF solutions only at a number of wavelengths. The optical effects from the inner layer has been recognized but could not be separated out from the main er effect by comparative measurements at two angles of incidence. This has been rationalized on the basis of similar variation of the er effect and the optical effect from the double-layer as a function of angle of incidence of light.     

Electron energy loss spectra of the silicon 2p, 2s, carbon 1s and valence shells of tetramethylsilane

Inner shell excitation spectra of tetramethylsilane, (CH₃)₄Si, have been measured in the silicon 2s, 2p (L_I,II,III-shell) and carbon is (K-shell) regions using electron energy-loss spectroscopy at an impact energy of 2.5 keV and a scattering angle of ~1°. The high-resolution valence shell spectrum has also been observed at an impact energy of 3 keV and a zero degree scattering angle. The silicon 2p spectra are compared and contrasted with published photoabsorption spectra of SiF₄, SiH₄, and other related Si-containing molecules with varying ligands.     

Photoelectron asymmetries and two-electron satellites near the 3p → 3d giant-resonance region in atomic Mn

The partial cross-sections and photoelectron angular distributions for several lines in atomic Mn have been measured at photon energies between 50 and 72eV. The intensities of the 3d correlation satellites at 24–26 eV binding energy behave similarly to the mainline intensity near the 3p → 3d giant resonance, but show an enhancement near the 3p threshold which is not present for the main line. A configuration-interaction analysis is applied to help identify the origins of the satellites. The 3p/3d branching ratio from 55–72eV and the shape of the 3d cross section in the resonance region are in good agreement with many-body perturbation-theory calculations.     

Surface composition of Fe-Al2O3 granular thin films by X-ray photoemission spectroscopy

X-ray photoemission Spectroscopy (XPS) results are presented which have given a direct insight into the surface composition of Fe-Al₂ O₃ “granular” thin films consisting of fine iron particles (φ ~ 40–150 Å) dispersed in an insulating alumina matrix. The data are mainly discussed in relation to: (i) the bulk iron content in the sample, (ii) the sample preparation procedure (e.g., by rotation of the sample target) and (iii) the mean iron particle size.At the surface, the iron is in a fully oxidized 3⁺ state within an alumina-rich partly hydrated region. Depth analysis, achieved by an Ar⁺ etching procedure, provides evidence of metallic iron and iron aluminate forms. In general, the metallic iron percentage increases with depth and with increasing iron bulk content.Good agreement is found between X-ray photoemission spectroscopy and Mössbauer Spectroscopy data. Fe²⁺ aluminate forms, which indicate an interaction between the metal particle and the alumina matrix, show increasing percentages with decreasing mean particle sizes.Particular attention is paid to evaluating the accuracy of XPS quantitative results, obtained by use of a first-principles model, and to assessing the importance of the artefacts associated with the Ar⁺ etching procedure.     

Vibrational and rotational energy transfer of CH+ in collisions with 4He and 3He

A quantum mechanical investigation of vibrational and rotational energy transfer in cold and ultra cold collisions of CH⁺ with ³He and ⁴He atoms is presented. Ab initio potential energy calculations are carried out at the BCCD(T) level and a global 3D potential energy surface is obtained using the Reproducing Kernel Hilbert Space (RKHS) method. Close coupling scattering calculations using this surface are performed at collision energy ranging from 10^-6 to 2000 cm^-1. In the very low collision energy limit, the vibrational and rotational quenching cross sections of CH⁺ in collisions with He are found to be of the same order of magnitude. This unusual result is attributed to the large angular anisotropy of the intermolecular potential and to the unusually small equilibrium value of the Jacobi R coordinate of the He–CH⁺ complex. As for the He–N₂ ⁺ collision, we also find a strong isotope effect in the very low collision energy range which is analyzed in terms of scattering length and the differences between these two collisions are also discussed.     

Study of excitation transfer Li (3 D → 3 P ) occurring in optical collisions with rare gas atoms experimentally

By selective optical excitation of collision pairs and observation of the reemitted fluorescence information is obtained on the role of the molecular channels involved in inelelastic collisions. As an example case we have studied experimentally the Li( 3 D → 3 P) excitation transfer in Li(3D)X systems with X = Ne, Ar by means of the optical collision process Li (2 P ) + X + h ν→ LiX (3 D Λ) → Li (3 P , 3 D ) + X where LiX (3 D Λ) collision molecules dissociate into Li(3P, 3D) atoms following laser excitation h ν of Li (2 P ) + X pairs. For this purpose we measured the Li 3P/3D population ratio by the fluorescence from these levels as function of the laser detuning Δν from the Li(2P-3D) transition and the rare gas pressure, and determined from this the 3P/3D excitation ratio B (Δν) for single collision conditions. The experiments were performed using two step cw laser excitation of gaseous mixtures Li + X at temperatures around 600 K in the detuning range |Δν| ? 100 cm^-1. The B (Δν) profiles obtained display strong blue-red wing asymmetries both for Li ^* Ne and Li ^* Ar. This reflects different dissociation probabilities from the 3 D Σ or 3 D (Π,Δ) states that are initially prepared by blue wing or red wing excitation, respectively. The results are qualitatively discussed in terms of new ab initio potentials for the two systems. Received 23 February 2000 and Received in final form 5 July 2000     

The role of photoelectronic processes in the formation of a fluorescent plume by 248-nm laser irradiation of single crystal NaNO3

 Visible fluorescent “plumes” are readily produced when nominally transparent ionic materials are exposed to pulsed UV laser irradiation. Over a wide range of laser fluences where plumes are observed, however, the photon and electron densities are inadequate to support multiphoton ionization and inverse bremsstrahlung, which are often used to explain plasma production and excitation of atomic spectral lines. We present evidence that the great majority of charged particles (electrons and positive ions) comprising the plume at the onset of formation in defect-laden NaNO₃ are emitted directly from the surface. A model is described wherein the required electron energy to excite and eventually ionize neutral atoms is provided by electrostatic interactions in the expanding plume. The time evolution of the “overlap” between the expanding charge cloud and thermally emitted neutrals accounts for the time evolution of the atomic line emissions after the laser pulse. Received: 15 August 1996/Accepted: 16 August 1996     

Photoluminescence characteristics of energy transfer between Er and Bi in Gd2O3: Er, Bi

The phosphors, Bi³⁺- activated Gd₂O₃:Er³⁺, were prepared by sol-gel combustion method, and their photoluminescent properties were investigated under ultraviolet light excitation. The emission spectrum exhibited sharp peaks at about 520, 535, 545, 550 and 559 nm due to (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions. The luminescent intensity was remarkably improved by the incorporation of Bi³⁺ ions under 340 nm light excitation, which suggested very efficient energy transfer from Bi³⁺ ions to Er³⁺ions. The introducing of Bi³⁺ ions broadened the excitation band of the phosphor, of which a new strong peak occurred ranging from 320 to 360 nm due to the 6s²→6s6p transition of Bi³⁺ ions. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Er³⁺ ions. Under 340 nm light excitation, Bi³⁺ absorbed most of the energy and transferred it to Er³⁺. The energy transfer probability from Bi³⁺ to Er³⁺ is strongly dependent on the Bi³⁺ ion concentration. Also, the sensitization effectiveness was studied and discussed in this paper.     

Trend of shape resonance-induced features in the angular distribution parameter as a function of photon energy for carbon,silicon and germanium tetrac

The angular distribution parameter as a function of photon energy, β(hν), has been measured in the 13–27 e V range using synchrotron radiation for the five valence orbitais in silicon and germanium tetrachlorides. The results have been compared with those previously reported for carbon tetrachloride. In particular, the trend of shape resonanceinduced features has been followed along the valence isoelectronic series CCl₄-SiCl₄-GeCl₄ for the 1e and 2t₂ orbitals. As the atomic number of the central atom increases, the shape resonances move toward the threshold ionization energy for a particular molecular orbital.