A theoretical investigation of titanium aluminium nitrides, (Ti,Al)N: Electronic structure and chemical bonding

Titanium aluminium nitrides, Ti_1-x Al _x N, can be prepared as films by various sputtering methods. They form metastable phases in which the titanium and aluminium atoms are randomlydistributed over the metal sublattice. In the present work two ordered model structures, Ti₃AlN₄ and TiAlN₂, have been chosen, for which LAPW band-structure calculations have been performed. The calculated densities of states (DOS) and the local partial DOS for both model structures are compared with the corresponding values for TiN. Characteristic changes in the DOS of the p band are observed which are caused by the nitrogenp orbitals that point towards the aluminium spheres. The bonding situation is investigated on the basis of electron density and difference electron density plots. The substitution of titanium atoms by aluminium atoms leads to stronger covalent Ti–Ti and N–Ti bonds and to additional ionic bonding contributions by the aluminium atoms whose ionicity increases from Ti_0.50Al_0.50N to Ti_0.75Al_0.25N.     

幻数尺寸Li-n-1,Lin,Li+ n+1(n=20,40)团簇的几何结构、电子与光学性质的第一性原理研究

基于密度泛函理论,采用第一性原理分子动力学模拟退火方法,对Li^-_n-1,Li_n,Li⁺_n+1 (n=20,40)的最低能量结构进行了全局搜索. 发现锂团簇的生长模式是以单个或多个嵌套的正多面体为核心,其余原子以五角锥为基本单元围绕核心生长. 基于最低能量结构的第一性原理电子结构计算得到锂团簇的分子轨道能级分布与无结构凝胶模型给出的电子壳层完全一致. 在总电 关键词： 团簇 电子结构 极化率 光吸收     

Stark broadening measurements of some N(II) and N(III) lines

The Stark widths of seventeen N(II) and ten N(III) spectral lines, emitted from a wall-stabilized arc plasma with electron densities in the range 0.9-2.9 × 10¹⁷ cm^-3, were measured. The arc was run with a 1:1N₂:He mixture, and the electron densities were determined from the Stark widths of He(I) 5876 and 6678 A. The Stark widths of the N lines were found to scale approximately linearly with electron density.     

8Li spin relaxation in liquid Li alloys with compound-forming tendency

In liquid Li-Bi, Li-Pb, Li-Sn and Li-Si alloys the spinlattice relaxation rate T ₁ ^–1 of -active⁸Li (T_1/2=0.8s) probe nuclei has been measured over wide concentration (c) and temperature (T) ranges. T ₁ ^–1 is governed by hyperfine contact interaction with the conduction electrons. Near the compositions Li₃Bi, Li₄Pb, Li₄Sn and Li₄Si both (T₁T)^–1 and d(T₁T)^–1/dT versus c show marked extrema. These data, when combined with Knightshift and/or conductivity values, inform on the prolongation of the electron residence time and the reduction of the density of states at the Fermi surface. There is progressive tendency to electron localization and compound formation in the sequence Li₄Pb, Li₄Sn, Li₃Bi with mainly ionic bonding in the case of liquid Li₃Bi.This work is sponsored by the Bundesministerium für Forschung und Technologie.     

Structure and luminescence of gadolinium-doped cubic boron nitride powder

The structural characteristics and chemical, morphological, and optical properties of cBN and cBN:Gd micropowders are studied by x-ray diffraction, energy-dispersive electron probe microanalysis (x-ray spectral microanalysis), and photoluminescence techniques. Cubic boron nitride (cBN) micropowders were synthesized at high pressures and temperatures from hexagonal boron nitride (hBN) micropowder and Li₃N catalyst. cBN:Gd micropowders were synthesized from mixtures of hBN, Li₃N, and GdF₃ micropowders. A lattice parameter of a~3.615 ? is calculated for both types of powder (cBN and cBN:Gd). The photoluminescence spectra of the cBN:Gd powder are found to contain emission lines attributable to intracenter optical transitions of Gd³⁺ ions.     

Electronic structure of silicon nitride according to ab initio quantum-chemical calculations and experimental data

Charge transfer ΔQ = 0.35e at the Si-N bond in silicon nitride is determined experimentally using photoelectron spectroscopy, and the ionic formula of silicon nitride Si₃^+1.4N₄^−1.05 is derived. The electronic structure of α-Si₃N₄ is studied ab initio using the density functional method. The results of calculations (partial density of states) are compared with experimental data on X-ray emission spectroscopy of amorphous Si₃N₄. The electronic structure of the valence band of amorphous Si₃N₄ is studied using synchrotron radiation at different excitation energies. The electron and hole effective masses m _e ^* ≈ m _h ^* ≈ 0.5m _e are estimated theoretically. The calculated values correspond to experimental results on injection of electrons and holes into silicon nitride.     

Ab initio calculations of endo-and exohedral C60 fullerene complexes with Li+ ion and the endohedral C60 fullerene complex with Li2 dimer

The results of ab initio Hartree-Fock calculations of endo-and exohedral C₆₀ fullerene complexes with the Li⁺ ion and Li₂ dimer are presented. The coordination of the Li⁺ ion and the Li₂ dimer in the endohedral complexes and the coordination of Li⁺ ion in the exohedral complex of C₆₀ fullerene are determined by the geometry optimization using the 3–21G basis set. In the endohedral Li⁺C₆₀ complex, the Li⁺ ion is displaced from the center of the C₆₀ cage to the centers of carbon hexa-and pentagons by 0.12 nm. In the Li₂ dimer encapsulated inside the C₆₀ cage, the distance between the lithium atoms is 0.02 nm longer than that in the free molecule. The calculated total and partial one-electron densities of states of C₆₀ fullerene are in good agreement with the experimental photoelectron and X-ray emission spectra. Analysis of one-electron density of states of the endohedral Li⁺@C₆₀ complex indicates an ionic bonding between the Li atoms and the C₆₀ fullerene. In the Li⁺C₆₀ and Li⁺@C₆₀ complexes, there is a strong electrostatic interaction between the Li⁺ ion and the fullerene.     

Electronic theory for the metal-non-metal transition in simple metal alloys

The metal-non-metal transition in liquid alloys such as Cs_1–x Au _x and Li_1–x Pb _x is explained as resulting from concentration dependent electron charge transfer causing short range atomic order and a change from metallic to ionic bonds. Numerical results for the electronic density of states, the electron charge transfer, the free energy of mixing and the volume change are given.     

First-principles study of high pressure phase transformations in Li<Subscript>3</Subscript>N

The lattice dynamics of lithium nitride (Li₃N) under high pressure are extensively investigated to probe its phase transformations by using the pseudopotential plane-wave method within the density functional theory. A new second order α↦α^′-Li₃N phase transition is identified for the first time. The newly proposed α^′-phase possesses a hexagonal symmetry with four ions in the unit cell having a space group of P-3m1. Further enthalpy and phonon calculations support the existence of this phase, which stabilizes in a narrow pressure range of 2.8 – 3.6 GPa at zero temperature. Upon further compression, transitions to denser packed phases of β-and γ-Li₃N are typical first order. The analysis of the electronic densities of states suggests that all the high pressure modifications of Li₃N are insulators and, interestingly, the typical behavior of compression is to broaden the band gap.     

Determination of the Concentration of Electrons in the Laser Plasma of Helium

The dependence of the Stark width of the spectral line of He II P 468.6 nm on the electron concentration in the laser plasma of helium for the range of electron densities N _e = (1–10)·10²³ m^–3 and electron temperatures of the order of 60 kK has been measured. The results obtained correspond well to Griem's theoretical data. An empirical relation is suggested which makes it possible to reliably determine the electron concentration from measured halfwidths in the investigated range of N _e.     

Measurement of excited state number densities of oxygen and nitrogen in a non-equilibrium plasma

Number densities of several excited states of atomic oxygen and nitrogen have been measured in the decaying non-thermal plasma of a θ-pinch afterglow. The spatial variation of the electron density and temperature as functions of time after initiation of main bank discharge have also been measured to facilitate a comparison of the excited state number densities with model calculations. Measurements of the atomic oxygen excited states indicate that quintet to triplet spin exchange collisions and doubly excited states must be included in the model. The measured populations of the excited atomic nitrogen states agree well with those calculated at high density (N_e≈ 10¹⁴ cm^?3), but disagree badly at lower densities (N_e ≈ 10¹² cm^?3). The discrepancies seem to be real since they are larger than expected measurement uncertainty.     

MW-ECR PE-UMS等离子体特性及对Zr-N薄膜结构性能的影响

采用静电探针技术对微波电子回旋共振(MW-ECR) 等离子体进行了诊断,利用等离子体增强 非平衡磁控溅射(PE-UMS)法在常温下制备了Zr-N薄膜, 通过EPMA，XRD，显微硬度对膜的 结构和性能进行评价.实验结果表明，随氮气流量增加，总的等离子体密度从807×10⁹c m^-3增加到831×10⁹cm^-3然后逐渐减小为752×10 ⁹cm^-3；而N₂⁺密度则从312×10^{8< /sup>cm-3线性递增到335×109cm-3；电子温度变化 不大.对薄膜而言，随N₂+密度增大，样品中氮含量增加，而晶粒逐 渐变小，当样品中N/ Zr原子比达到14时，薄膜中出现亚稳态的Zr₃N₄相以及非晶相， 在更高氮流量下，整 个薄膜转变为非晶态.与此相应，薄膜硬度由最初的225GPa增大到2678GPa 然后逐渐减 小到1982GPa. 关键词： 氮化锆薄膜 ECR等离子体 磁控溅射 诊断}     

Path integral approach for Stark broadening of Lyman lines in hydrogen plasma

New results for Lyman lines from hydrogen plasmas are presented using the path integral approach. The influence of plasma components (electrons and ions) on the radiator is analysed separately. The ionic contribution is treated within the path integral approach, while the electronic contribution is estimated by the standard collision operator. The Stark effect, including the ion quadrupole contribution, is considered. The time‐dependent ionic microfield is treated within the path integral approximation using the model microfield method (MMM). The comparison with the quantum statistical approach is performed using a wide range of temperatures (T = 10⁴–10⁷ K) and electron densities (N_e = 10²³–10²⁶ m^?3). Good agreement is mainly obtained for low density and high temperature.     

ESR studies on the pressure and temperature dependence of electron self-exchange kinetics between tetrathiafulvalene (TTF) and its radical cation in ionic liquids and organic solvents

The question whether chemical reactions and diffusion processes in ionic liquids are comparable with those taking place in classical organic liquids is a current issue in the literature. Pressure- and temperature-dependent investigations on simple electron self-exchange reactions between the two partners of a redox couple are good tools to get a better understanding of how the solvent influences such reactions. The electron self-exchange reaction between tetrathiafulvalene (TTF) and its radical cation has been investigated in two ionic liquids and two organic solvents using electron spin resonance (ESR) line broadening experiments at variable temperature and pressure. Rate constants are reported for the ionic liquids 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim⁺][Tf₂N^?]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim⁺][Tf₂N^?]) within a temperature range of 298 K ≤ T ≤ 368 K and a pressure range of 0.1 MPa ≤ p ≤ 100 MPa. The self-exchange reaction of the redox couple [TTF/TTF^?+] has been found to be diffusion-controlled in the used ionic liquids over the entire temperature range. The observed rate constants in ionic liquids at higher pressures are larger than those predicted by common diffusion, and suggest that the electron transfer takes place within a solvent cage. Also, the self-exchange reaction of the [TTF/TTF^?+] redox couple in classical solvents (dimethylphthalate (DMP) and acetonitrile) was investigated and compared to the results with those obtained in ionic liquids. The high viscosity of the ionic liquids makes it difficult to extract the electron transfer rate constants reliably, making interpretation within the framework of the Marcus Theory impossible.     

Electronic structure and binding mechanism of Cu2O

A self-consistent LAPW band structure calculation of Cu₂O is presented. Total and partial densities of states and electron densities were calculated and are used to give an interpretation of chemical bonding. It is found that there are significant deviations from a simple ionic picture due to a depletion of the valence band of Cu-3d electrons leading to a non-spherical charge density around Cu. A critical discussion of theoretical and experimental work on Cu₂O is given.     

(Li3N)n(n=1—5)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Li₃N)_n(n=1—5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构. 并对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究. 结果表明,(Li₃N)_n(n=1—5)团簇中N原子的配位数以4,5较多见,Li—Li键长为0.210—0.259nm,Li原子在桥位时Li—N键长为0.185—0.204nm,Li原子在端位时Li—N键长为0.172—0.178nm;团簇中N原子的平均自然电荷为-2.01e,Li原子的平均自然电荷为+0.67e;Li₃N,(Li₃N)₅团簇有相对较高的动力学稳定性. 关键词： 3N)_n(n=1—5)团簇')" href="#">(Li₃N)_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

Wavepacket dynamics and quantum mechanical energy densities in the quartet N+ 2 + O2 system

Surface crossing of the potential energy surfaces (PESs) and the formulation of differentiable PES functions are discussed in the quartet N⁺ ₂ + O₂ system containing the T shape intermediate complex. Consideration of the ion-dipole interaction between N₂ and O₂ fragments due to the induced dipole moment of the neutral molecule gives a good image of the surface crossing between the quartet reactant state (N⁺ ₂ ···O₂) and the quartet product state (N₂ ···O⁺ ₂) for the charge transfer (CT) reaction in terms of the conventional harpooning mechanism. Differentiable functions of PESs are constructed for the reactant and product states that may be applied for 3-dimensional dynamics calculations by means of wavepackets, and examples of 2-dimensional wavepacket dynamics calculations are introduced. Further, electron transfer processes and local electronic nature in the CT reaction are discussed in terms of the quantum mechanical energy densities based on regional density functional theory. Regional partitioning by using the kinetic energy density provides a new concept of electron transfer, and the tension density provides new images of microscopic electronic stresses.     

Effect of <Superscript>14</Superscript>N Nucleus Capture in Nuclear Quadrupole Resonance at Small Relaxation Parameters

Experiments on detecting induction signals of nuclear quadrupole resonance (NQR) on ¹⁴N nuclei in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ (RDX) with preliminary changed population densities of NQR energy levels upon exposure to a saturating pulse are described. It is demonstrated that this actually causes the induction signal amplitude to change; however, complete saturation of the transition cannot be reached because of the NQR relaxation time. It is also demonstrated that the results of calculations without regard for the relaxation processes in RDX lack experimental support. Experimental data demonstrate the feasibility of application of the methods of preliminary change of the population densities (by pumping) for multifrequency experiments in NQR and explosive detection.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 49–52, April, 2005.     

Phonon spectra and lattice dynamics of lithium nitride

Lithium nitride, Li₃N, belongs to the hexagonal structure with the symmetry point group D_6h. The structure is ionic with four atoms per unit cell and N^3- coordinated in a regular way with eight Li⁺ ions. Polarized Raman scattering and infrared reflectivity spectra are reported. The frequencies of zone center phonons are determined from a Kramers-Kronig analysis and the oscillator fits to the reflectivity data. A rigid shell model with eight parameters, including the anisotropic polarizability of nitrogen ions, yields an excellent fit to the observed phonon frequencies.     

Chemical Bond in Metal Azides and Their Reactivity

Results of experimental investigations into the processes of slow and explosive decomposition of metal azides and the corresponding phenomenological models are analyzed. The energy-band structure and the valence electron density for actual crystallographic planes as well as the hypothetical electron density of the first unoccupied band of KN₃ and AgN₃ are calculated by the density functional method with the use of pseudopotentials. It is demonstrated that the anion-cation chemical bond in KN₃ is predominantly ionic in character, whereas a significant covalent component in AgN₃ is caused by Ag d-states. From the character of distribution of the valence and hypothetical electron densities it follows that the exciton and vibron decomposition mechanisms are improbable. The chain process is also improbable for alkali metal azides, because the gap energy for them is E _g 8 eV, which is close to the energy of azide ion decomposition Q 9–12 eV; the chain process is probable for AgN₃, because E _g(AgN₃) 3 eV. The chain process in AgN₃ is also favored by intense delocalization of the valence electron density through the hybridization of the Ag d-state and the N p-state, which causes a relatively high hole mobility.