Optical characterization of the phosphate glasses containing pair transition ions

The paper deals with optical and electronic properties of the aluminophosphate glasses containing Fe–Mn and Fe–Cr ion pairs in different concentration. The influence of the mixed alkali ions over the electronic properties has been investigated. The optical behavior (optical transmission) of the glass samples has been studied by UV-VIS spectroscopy and the refractive index dependency on wavelength has been discussed. The transmission spectra show features specific for the doping transition ions (TM), revealing different oxidation states of iron (Fe²⁺/Fe³⁺), manganese (Mn²⁺/Mn³⁺) and chromium (Cr³⁺/Cr⁶⁺) in the vitreous network. Mössbauer spectroscopy offers information regarding the TM oxidation states, redox processes and the iron coordination symmetry in the vitreous network. In the case of Fe–Mn doped glasses, the percentage of Fe²⁺ is about 40% and a doubled iron content leads to an increasing of Fe²⁺ percentage up to 53%. The replacing of lithium ions by natrium ions (mixed alkali effect) provides an increasing of the Fe²⁺ percentage up to 56%. The occurrence of the tetrahedral or octahedral symmetry of Fe²⁺ ions bonded by O^2? ions depends on the transition ion nature and Li⁺/Na⁺ ratio. Infrared absorption spectra of the pair transition ions-doped aluminophosphate glasses reveal optical phonons specific for the phosphate glass matrix.     

Quasi-ordered nanostructures on the surface of strontium titanate

The results of the investigation of the surface of strontium titanate single crystals after treatment with high-energy plasma are presented. The surface morphology of the strontium titanate single crystals and the change in its characteristics after plasma treatment have been studied using electron scanning and atomicforce microscopy. A change in the electronic state of a part of the titanium ions and a change in the stoichiometry in the modified near-surface layer have been found by the method of valence shift of X-ray lines. A preliminary analysis has been made of the conditions providing the formation of single- and two-level systems of ordered crystallites with sizes of 10⁻⁷–10⁻¹⁰ m on the surface of single-crystal strontium titanate with impurities of ions of the iron and lanthanum groups.     

Investigation of Glasses and Glaze Coats of Composition R2O–RO–Fe2O3(FeO)–Al2O3–B2O3–SiO2 by the EPR Method

The valence state and the coordination environment of the paramagnetic centers of iron ions in glasses and vitreous coats of composition R₂O–RO–Fe₂O₃(FeO)–Al₂O₃–B₂O₃–SiO₂ have been investigated by the EPR method. The tetrahedral and octahedral coordinations of Fe³⁺ ions have been revealed. The character of change in the EPR spectra of the materials studied in the vitreous and vitrocrystalline state has been determined. It is shown that the coordination number of iron ions is dependent on the crystallization processes.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Understanding the Effects of Point Defects on the Electronic Properties of Titania Nanoparticles: An Ab Initio Study

First-principles calculations are used to study the electronic structure of the TiO₂(101) surface. The effect of oxygen vacancies and interstitial titanium ions on the electronic structure is investigated, and models for optical single-electron charge transfer transitions in the structure are proposed. We found that the addition of an uncharged oxygen vacancy leads to a shift of the total density of states toward lower energy, and the bandgap increases. Therefore, interstitial titanium ion incorporation induces donor states above the valence band and increases the bandgap. These results can be used to explain the observed blueshift in nanoscale TiO_2.     

Configuration Interaction and Many‐Body Perturbation Theory: Application to Scandium,Titanium, and Iodine

A number of atoms and ions with complex valence configurations are considered as candidates for atomic clocks with high sensitivity to the possible variation of the fine‐structure constant. Present level of the theory is not sufficient to predict frequencies of the clock transitions with accuracy, required for the experiment. Here an approach is tested, where the second‐order perturbation theory is used to iteratively saturate configuration space for valence electrons. On the examples of scandium, titanium, and iodine, it is demonstrated that this improves the efficiency of the CI+MBPT method for systems with strong configuration interaction and/or more than three valence electrons.     

Ab initio simulation of the influence of zirconium impurity ions on the atomic and electronic structure of BaTiO<Subscript>3</Subscript>

The influence of zirconium impurity ions on the atomic and electronic structure of cubic barium titanate is studied theoretically by the electronic density functional theory and pseudopotential theory. It is shown that Zr ions induce local distortions in the BaTiO₃ lattice, although neither zirconium nor titanium ions shift from their ideal positions, so that the structure of BaTi_{1 − x} Zr _x O₃ compounds remains cubic. The introduction of zirconium in an amount of 37.5 at % broadens the energy gap by 0.18 eV.     

Thermal conductivity degradation induced by heavy ion irradiation at room temperature in ceramic materials

The thermal conductivity degradation induced by irradiation with energetic heavy ions at room temperature is studied and quantified. Three semi-metallic systems: titanium and zirconium carbides, titanium nitride, as well as a covalent compound: 6H silicon carbide were irradiated by 25.8 MeV krypton ions at 10¹⁶ and 6 . 10¹⁶ ions.cm^-2 doses to produce defects. During ion irradiation, inelastic collisions and elastic collisions occur at a different depth in a material. Two collision domains can be defined. Modulated thermoreflectance microscopy measurements were performed at differing frequencies to characterize the thermal conductivity degradation in these two domains for each of the investigated materials. Our results reveal a significant thermal conductivity degradation in the two collision domains for all materials. Elastic collisions are shown to degrade more strongly the thermal properties than inelastic ones. Scattering of thermal energy carriers is larger in elastic collision domain because displacement cascades produce a very high concentration of point defects: vacancies, interstitials and implanted Kr ions. The degradation coming from electronic interactions that seems to be more important in SiC can be explained by the presence of large populations of generated extended defects, facing to generated individual point defects in TiC, TiN or ZrC.     

First-principles studies of zigzag pristine boron nitride nanotubes doped with one iron atom

Interaction of one iron atom with pristine zigzag boron nitride nanotubes with different diameters, ranging from (8,0) to (12,0), have been investigated using density functional theory calculations. Departing from four initial configurations, considering each of them interacting with the tubes’ walls either from inside or outside, we have analyzed the adsorbate migration to the most favorable positions together with the related binding energies and the equilibrium distances as well as the electronic structure of the final systems. It was observed that the smaller the radius of the tube the lower is the binding energy for all studied structures, and also that the inner configuration is more stable than the outer one for small radius. For the preferred position for the iron atom, it was seen that it varies according to the starting configuration and that the iron-first-nitrogen-neighbor bond length works as a constraint in determining the most favorable position for the adsorbate. Finally, for the electronic structure, it was observed that the presence of the dopant introduces localized levels at the band gap of the nanotubes and that those levels are mostly related to the orbitals 3d and 4s of the iron atom. For the inside case, as a consequence of higher hybridization and a confinement effect, the gap closure is more pronounced for small diameter tubes. For all studied structures, it was observed a net-spin-polarization equal to 4 μ _B.     

Aspects of the identification of iron oxidation states by Mössbauer isomer shifts

A hypothesis based on the literature data on the Mössbauer, structural, and magnetic parameters of different iron oxidation states is proposed, according to which changes in the electronic configuration of an iron ion that are caused by an electron (or a change of iron oxidation state by one) can vary the isomer shift by a constant (~0.33 mm s^?1), if it is assumed that the structure of the iron’s valent shell and iron spatial environment remain unchanged.     

The role of the hydration configuration in electronic processes involving ions in aqueous solution

The nature of small ions in electrolytic (e.g., aqueous) solutions is discussed in terms of the configuration of the adjoining polarized medium, and the role of this configuration in electronic transitions involving one or a pair of ions is treated in a general way. Light absorption by a single ion is shown to depend critically on this configuration; a theory developed previously by the authors is reviewed, and future possibilities of exploring the nature of the configuration by investigation of such spectra are explained. Electronic transitions, such as an “electron transfer” process, during binary collisions of ions are treated, and a general method is developed, based uponDebye's “diffusion” theory for ion collision rates and a nonadiabatic type of potential curve. Rates of chemical processes are found to depend decisively on the interaction of two ions at separations where the simple coulomb law is not valid.     

Effective sputtering yields of titanium,titanium nitride,and molybdenum induced by nitrogen ions and ions of nitrogen-oxygen mixtures

This work is dedicated to studying the effects of nitrogen ions and ions of nitrogen and oxygen mixtures on the surface of titanium, titanium nitride, and molybdenum. The usage of magnetron sputtering systems as a model device to study the effect of reactive gases on elements of electric jet engines is proposed and justified. The processes of sputtering of a surface exposed to non-monoenergetic ion beams are studied. The effective sputtering yields of titanium, titanium nitride, and molybdenum induced by argon and nitrogen ions and ions of nitrogen-oxygen mixtures at various intermediate-energy ion beams are determined. It is shown that the sputtering yields of reactive-gas ions are significantly lower than the sputtering yields of inert gases.     

铁小檗碱化合物结构的密度泛函理论研究

本工作采用密度泛函理论(B3LYP)方法对铁小檗碱化合物的中性分子及离子进行了结构优化和频率计算.结果表明:无论是中性分子还是离子,铁小檗碱物化合物基态结构都是小檗碱基态结构中的与N原子相邻的C10原子上键合一个Fe原子形成的.其阳离子结构具有C_1对称性和~3A电子态;中性分子的基态结构具有C_1对称性和2A电子态;阴离子的基态结构具有C1对称性和5A电子态.当铁小檗碱物化合物的阳离子得到一个电子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所变短;当中性分子得到一个电子变成阴离子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所增加.     

铁小檗碱化合物结构的密度泛函理论研究

本工作采用密度泛函理论（B3LYP） 方法对铁小檗碱化合物的中性分子及离子进行了结构优化和频率计算。结果表明:无论是中性分子还是离子,铁小檗碱物化合物基态结构都是小檗碱基态结构中的与N原子相邻的C10原子上键合一个Fe原子形成的。其阳离子结构具有C1对称性和3A电子态;中性分子的基态结构具有C1对称性和2A电子态;阴离子的基态结构具有C1对称性和5A电子态。当铁小檗碱物化合物的阳离子得到一个电子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所变短;当中性分子得到一个电子变成阴离子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所增加。     

高电荷态离子Arq+与不同金属靶作用产生的X射线

研究了高电荷态离子Ar^q+(q=16，17，18)入射金属Be，Al，Ni，Mo，Au靶表面产生的X射线谱.实验结果表明，Ar的Kα-X射线是离子在与固体表面相互作用过程中固体表面之下形成空心原子发射的.电子组态1s²的高电荷态Ar¹⁶⁺离子在金属表面中性化过程中，存在的多电子激发过程使Ar¹⁶⁺的K壳层电子激发产生空穴，级联退激发射Ar的Kα 特征X射线.Ar¹⁷⁺离子在金属表面作用过程中产生的X射线谱形与靶材料没有明显的关联,入射离子的Kα-X射线产额与其最初的电子组态有关，靶原子的X射线产额与入射离子的动能有关. 关键词： 高电荷态离子 空心原子 多电子激发 X射线     

Simulation of the atomic and electronic structures of mesoporous SiO2 containing Ti4+ and Zr4+ ions

The influence of Ti and Zr impurity atoms on the atomic and electronic structures of a mesoporous SiO₂ matrix is ab initio simulated in a generalized gradient approximation. Energetically favorable positions of titanium and zirconium in the structure are revealed. The incorporation of Zr and Ti ions is shown to decrease the bandgap.     

Iron nanoparticles in amorphous SiO<Subscript>2</Subscript>: X-ray emission and absorption spectra

The local structure of the chemical bond of iron ions implanted into SiO₂ glasses (implantation energy, 100 keV; fluence, 1 × 10¹⁶ cm^?2) is investigated using x-ray emission and absorption spectroscopy. The Fe L x-ray emission and absorption spectra are analyzed by comparing them with the corresponding spectra of reference samples. It is established that iron nanoparticles implanted into the SiO₂ vitreous matrix are in an oxidized state. The assumption is made that the most probable mechanism of transformation of iron nanoparticles into an oxidized state during implantation involves the breaking of Si-O-Si bonds with the formation of Si-Si and Fe-O bonds.     

离化态原子的电子结构

本文利用相对论性Dirac-Slater自洽场方法,系统地分析了原子序数小于等于95的所有中性原子和离化态原子的基态电子结构,并讨论了电子组态间存在的竞争,以及轨道屏蔽系数的平滑性和“准”可加性。本文结果将是进一步系统精确地探讨原子和离子电子结构的基础,同时根据本文结果,能方便地建立有关的原子物理数据库,可满足应用方面的需要。 关键词：     

On the compensation of heterovalent ferric ions in the lattice of barium titanate single crystals

The introduction of heterovalent ferric ions into the titanium sites of the BaTiO₃-lattice of single crystals prepared by the fluoride process is due to the formation of oxygen vacancies and to the introduction of F-ions into the oxygen sites. Experimental results obtained by physical and chemical methods show the dependence of both mechanisms of compensation on the iron content of the crystals.     

Response of La0.8Sr0.2CoO3-δ to perturbations on the CoO3 sublattice

Emission and transmission M?ssbauer studies of La_0.8Sr_0.2CoO_3-δ perovskites doped with ∼0.02 stoichiometric units of oxygen vacancy or 2.5% iron corroborate the occurrence of electronic phase separation in these systems. The effect of the small perturbation of the CoO₃ sublattice with either iron ions or oxygen vacancies on the bulk magnetization as well as on the M?ssbauer spectra is in good agreement with the double exchange based cluster model. The magnetoresistance does not show any peak near the Curie temperature, but reaches -84% in a field of 7.5 T at T = 8 K. Below T_C ≈ 180 K the M?ssbauer spectra distinctly include the contribution from paramagnetic and ferromagnetic regions, providing direct evidence for phase separation. No contribution to the spectra from Fe⁴⁺ ions can be observed, which is an unambiguous evidence that at low concentration iron (either directly doped or formed from ⁵⁷Co by nuclear decay) is accommodated in the cobaltate lattice as Fe³⁺ ion.