Energy transfer between Ln(III) ions in aqueous solutions upon formation of labile binuclear fluoride and nitrate complexes of these ions

The influence of anions on nonradiative electronic energy transfer between lanthanide ions in aqueous solutions is studied. The rate constant k _t of energy transfer was found to increase by three orders of magnitude upon addition of salts of hydrofluoric acid to the solution. This effect is caused by the formation of bridge labile binuclear complexes, an excited energy donor-fluorine anion-acceptor, which increase the encounter time between a donor and an acceptor, resulting in the increase in the probability of energy transfer. The independence of k _t of the Förster overlap integral in the bridge complex containing F^? was explained by the fact that energy transfer occurs in each event of the binuclear complex formation, the maximum rate constant of energy transfer being equal to the rate constant of the binuclear complex association. Bridge complexes formed via the NO ₃ ^? anion are also considered. These binuclear complexes are unstable, and k _t for them is proportional to the Förster overlap integral. In this case, energy transfer occurs not during each event of the complex formation. This allows us to estimate the lower limit of the dissociation constant of the binuclear complex and its stability constant. Thus, the study of influence of various anions on energy transfer represents a new efficient luminescent method for analysis of properties of labile binuclear complexes in solutions.     

Ab initio configuration interaction study on the electronic structure of the X2Σ+, B2Σ+ and 32Σ+ states of SiO+

The energy levels and electronic structure of the X²Σ⁺, B²Σ⁺ and 3²Σ⁺ states of SiO⁺ are studied using ab initio configuration interaction (CI) calculations at and around their equilibrium internuclear distances R _e. Spectroscopic constants and the vertical excitation energy from the SiO⁺ X²Σ⁺ state are predicted for the 3²Σ⁺ state. Based on the calculated CI wavefunctions, avoided crossings of the potential energy curve for the 3²Σ⁺ state and a near-degeneracy effect in the avoided crossing region are examined. The effects of the mixing of excited configuration state functions in the total electronic wavefunctions for the 1–3 ²Σ⁺ states are investigated by analysing correlation energies in terms of the contributions from classes of excited configurations. The importance of both the near-degeneracy effect and the correlation energy effect in describing correctly the electronic structure of the 3 ²Σ⁺ state in the neighbourhood of its R _e is discussed.     

等离子体效应对类氦氖Kα线系电偶极辐射的影响

采用离子球模型，通过自洽求解Boltzmann方程和Poisson方程，得到类氦氖离子Kα线系的两条电偶极辐射光谱能量随等离子体环境的漂移.结果显示，Kα线系电偶极谱线随等离子体电子密度增大发生红移，红移量与等离子体电子密度有近似的正比关系；随着等离子体电子温度的降低，光谱红移对等离子体电子密度的敏感性增大.另外，所研究的两条谱线间的能量间隔随等离子体电子密度的增大而减小，减小量随等离子体电子密度的变化也呈现出近似的线性规律.值得注意的是，类氦氖Kα线系中两条电偶极谱线分别为互组合线与共振谱线，而其能量差就是1s2p(³P₁)的交换能，因此进一步发现能级中交换能将随等离子体环境变化的规律.所观察到的光谱红移和精细结构分裂在高密度等离子体中都有明显的变化，对探索高密度等离子体的诊断新方法有重要意义. 关键词： 光谱漂移 交换能 等离子体 类氦离子     

Simultaneous effects of temperature and pressure on diamagnetic susceptibility of a shallow donor in a quantum antidot

The effect of temperature and pressure, simultaneously, on the diamagnetic susceptibility and binding energy of a hydrogenic donor impurity at the center of a GaAs/Ga_1−xAl_xAs quantum antidot is studied within the effective mass approximation. For this goal, we first analytically solve the Schrödinger equation to obtain wavefunctions and energy levels. Then, using the electronic states, we can calculate the diamagnetic susceptibility. The results obtained from the present work reveals that (i) the diamagnetic susceptibility increases with increasing pressure, (ii) the diamagnetic susceptibility decreases by increasing temperature, (iii) the value of 〈r²〉 decreases with increasing pressure due to the quantum confinement, and (iv) an increase in the pressure enhances the binding energy for a constant temperature.     

A quasiclassical study of collisions of He with HD(B 1Σ+ u )

A quasiclassical trajectory study has been carried out for collisions of ⁴He with electronically excited H₂(B ¹Σ⁺ _u ) and its isotopomer HD. By using analytical fits for the ab initio potential energy surfaces of the ground and the excited state we have obtained vibrational and electronic quenching cross sections for several initial conditions. We draw the following conclusions. Vibrational excitation strongly promotes electronic quenching whereas translational energy is less effective. Rotational excitation decreases the rate of quenching. In a remarkable contrast to the ground electronic state, vibrational energy transfer on the excited potential energy surface is an efficient and fast process. Collisions at high energies results in T → R energy transfer. The above conclusions are valid for both H₂ and HD.     

Electronic energy levels of CsCdCl3

The excitation and emission spectra of CsCdCl₃ crystal grown by the Bridgman growth technique, are observed. Its dominant excitation spectra correspond to the transitions between the electronic energy levels of the face-shared [CdCl₆]⁴⁻ octahedron complexes with C_3v symmetry. With the help of the molecular orbital diagram of the [CdCl₆]⁴⁻ molecule complex, an approximate electronic energy level diagram of this crystal is constructed using one-electron approximation.     

Study of intermixing and Zr-silicide formation using swift heavy ion irradiation

Swift heavy ion (SHI) beam induced irradiation is an established technique for investigating structural modifications in thin films depending on the S _e sensitivity of material. Intermixing due to 120 MeV Au ion irradiation at different fluences from 10¹² to 10¹⁴ ions/cm² has been reported as a function of ion fluence in a-Si/Zr/a-Si thin films on Si substrate. The samples are characterized before (pristine) and after irradiation using Grazing Incident X-ray Diffraction (GIXRD) and Rutherford Backscattering Spectroscopy (RBS), which confirm the formation of ZrSi at thin film interface. It is suggested that mixing is mainly due to electronic energy loss since the energy transferred from high energy ions seems to create a transient molten zone along the ion track. It is found that the interface mixing increases linearly with the increase in ion fluence. The mixing effect explained in the framework of Thermal spike model. The irradiation effect on the surface roughness of the system is measured using Atomic Force Microscopy (AFM) technique. The current conduction mechanism and Schottky barrier height are also calculated by taking I–V curves across the Metal/Si junction.     

化合物和合金中离子投影射程分布矩的计算(Ⅱ)——轻离子(Z1≤10)的射程分布矩

本文根据离子在固体材料中电子阻止截面的实验资料,给出了低能Li⁺,Be⁺,B⁺,C⁺,N⁺,O⁺,F⁺,Ne⁺等离子在固体中电子阻止截面S_e的经验公式。这些经验公式既能够很好地反映电子阻止本领的Z₁和Z₂振荡、又能正确地给出S_e随离子能量E的变化关系。用这种以实验为基础的S_e经验公式和符合于WHB势的核散射函数,计数了从H⁺到Ne⁺十种轻离子在非晶Al₂O₃,SiO₂,20/25/Nb不锈钢,LiNbO₃和UO₂等材料中的投影射程分布的一次至三次矩。将计算值与近几年的实验测量及其他人的计算结果进行了比较,在低能端,我们计算的平均投影射程R_p与实验符合得更好。 关键词：     

Perturbative upper bounds for the electronic energy of diatomic molecules from level-set boundaries of nuclear charge space

Simple bounds to the electronic energy of diatomics are obtained using curvature properties in the space of nuclear charges. The bounds present the same analytic structure in terms of the internuclear separation as the exact electronic energy. They are determined from a single-atom property and can be improved using perturbative expansions of the energy. The approximate continuation of the large-R perturbation series for the electronic energy of H₂⁺ is discussed as an illustrative example.     

Dependence of the Er<Subscript>2</Subscript>O<Subscript>3</Subscript> selective emission on the intensity of laser thermal excitation

The dependence of the selective emission (SE) spectra of erbium oxide (Er₂O₃) in the visible and near-IR spectral ranges on the laser excitation intensity at a wavelength of 10.6 μ m is experimentally studied. The intensity ratio for the Er³⁺ electronic and vibronic transitions in the SE spectra is varied with an increase in the laser intensity to 10 kW/cm². The mechanism for the multiphonon fluctuation excitation of electronic states and a possibility for the SE application in the observation of the thermo-photo-laser effect are discussed.     

Structural analysis and band gap tailoring of Fe3+-doped Zn–TiO2 nanoparticles

We report on the analysis of morphology and electronic structure of Fe³⁺-doped Zn–TiO₂ nanoparticles. Crystalline nature, phase, and preferred growth direction of the nanoparticles were all determined. Due to size effects and OH⁻–(TiO₄) ⁿ complexes, variation in the energy gap with metallic and semiconducting characters on the same sample was found. The variation in the energy gap decreased, and the bang gap decayed exponentially with Fe doping and independent of the supporting substrates. Simultaneous effect of the OH⁻ ligands on the electronic structure and the formation mechanism of nanorods and nanosheets as manifested by the rutile TiO₆ octahedra units edge- and corner-shared bonding was discussed.     

从头计算研究BCl+基态和激发态的势能曲线和光谱性质

基于相关一致极化4zeta(aug-cc-pVQZ)基组, 应用量子化学从头计算中高水平的多参考组态相互作用方法计算了BCl⁺ 两个离解极限B⁺(¹S_g)+Cl(²P_u)和B (²P_u)+Cl⁺ (³P_g)的14个Λ-S态势能曲线. 在计算中考虑了Davidson修正(+Q)和标量相对论效应, 并首次在计算中考虑了BCl⁺ 的旋轨耦合效应, 获得了由能量最低的4个Λ-S态分裂出的7个Ω 态. 计算结果表明相同对称性的Ω 态的势能曲线存在着非常明显的避免交叉. 通过分析Λ-S态的电子结构, 得到了各态的电子跃迁特性, 并确认了电子态的多组态性质. 使用LEVEL程序通过求解径向的Schrödinger方程得到了束缚Λ-S 和Ω态的光谱参数D_e, R_e, T_e, ω_e, ω_eχ_e和B_e. 通过和已有的Λ-S态X²∑⁺ 的实验数据进行对比发现, 本文所得的计算结果与实验结果非常一致. 而文中其他电子态的光谱参数均为首次报道. 关键词： 势能曲线 光谱参数 多参考组态相互作用方法 旋轨耦合     

二价金属元素掺杂对LiCoO2体系电子输运性质的影响

为了解释Ca掺杂与Mg掺杂在影响锂离子二次电池正极材料LiCoO₂体系电子输运性质方面的不同效应，采用基于密度泛函理论的第一性原理方法研究了该体系的电子结构.计算结果表明，虽然在LiCoO₂体系中用Ca或Mg替代Co都会在费米能级附近产生部分占据的受主带，但两者对应的电子态都具有明显的局域化特征；此外，与Mg掺杂体系明显不同的是，Ca掺杂体系的受主带与价带之间存在清晰的带隙.这一带隙的存在正是Ca掺杂不能明显提高LiCoO₂体系电导率的主要原因.此外，Ca²⁺与Mg²⁺离子半径的较大差别也是造成这两个掺杂体系的电导率存在明显差异的一个重要因素.     

Impact of Ultrathin Pb Films on the Topological Surface and Quantum-Well States of Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Topological Insulators

The effect of an ultrathin Pb film deposited on the surface of Bi₂Se₃ and Sb₂Te₃ compounds on the electronic state structure of topological insulators is studied experimentally by the angle-resolved photoemission spectroscopy (ARPES) technique. The following features are revealed: formation of two-dimensional quantum-well states in the near-surface region, an increase in the binding energy of the Dirac cone and the core levels, and a simultaneous electronic states intensity redistribution in the system in photoemission spectra. The results obtained show that topological states may coexist at the interface between studied materials and a superconductor, which seems to be promising for application in quantum computers.     

Photoluminescence of Ca(Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> compounds

Photoluminescence (PL) observed in solid solutions of Ca(Al _x Ga_1–x )₂S₄:Eu²⁺ (x = 0.1–0.3) is studied. It is shown that the increase in emission intensity by 18% is caused by changes in the x values and electronic 5d → 4 f transitions in Eu²⁺ ions. A change in the position of the emission spectrum or its partial shift toward shorter wavelengths is due to an increase in the aluminum concentration and a decrease in the crystal field energy. The energy of the zero phonon line E ₀, redshift D, and the Stokes shift ΔS are determined. A decrease in the photoluminescence intensity maximum and an increase in the half-width of the spectrum are found in the temperature range of 10–300 K. The efficiency of emission at temperatures of 20 and 300 K is almost independent of the excitation power density of up to ~10⁴ W/cm². The luminescence lifetime of Eu²⁺ ions was 383, 357, 346, and 333 ns for x = 0, 0.1, 0.2, and 0.3, respectively.     

Effect of the long-range order in the vacancy distribution on the electronic structure of titanium monoxide TiO1.0

The effect of the long-range order in the vacancy distribution according to the type of monoclinic Ti₅O₅ superstructure on the electronic structure of titanium monoxide TiO _y with the stoichiometric composition has been studied by the supercell method within the DFT-GGA approximation with the use of pseudopotentials. It has been established that, in spite of an increase in the Fermi energy, the stability of the compound increases with increasing degree of the long-range order η. The ordering of the structural vacancies leads to the considerable increase in the depth of the pseudogap at the Fermi level. It has been shown that the effect of the long-range order on the electronic structure in the range of η from 0 to 1.0 is much weaker than the effect of the nonstoichiometry of TiO _y in the range of y from 0.75 to 1.33.     

Density function study transition metal chromium-doped alkali clusters: the finding of magnetic superatom

The structures, stabilities and magnetic properties of CrX_n (X = Na, Rb and Cs; n up to 9) clusters are studied using density functional theory to search for the stable magnetic superatoms. The geometrical optimisations indicate the ground-state structures of CrX_n evolve toward a close packed structure with an interior Cr atom surrounded by X atoms as the cluster size increase. Their stabilities are analysed by the relative energy, gain in energy (ΔE(n)) and the highest unoccupied molecular orbital and lowest unoccupied molecular orbital gaps. Furthermore, the magnetic moments of CrX_n clusters show an odd–even oscillation. Here, we mainly focus on the CrX₇ (X = Na, Rb and Cs) clusters due to the same valence count as the known stable magnetic superatoms VNa₈, VCs₈ and TiNa₉. Although these clusters all have a filled electronic configuration 1S²1P⁶ and large magnetic moment 5 μ_B, our studies indicate that only CrNa₇ is highly stable compared to its nearest neighbours, while CrRb₇ and CrCs₇ clusters are less stable. This suggests that Cr-doped Na₇ is most appropriate for filled electronic configuration and CrNa₇ is shown to be a stable magnetic superatom. More interesting, we find CrRb₈ and CrCs₈ with the filled electronic configuration 1S²1P⁶ have higher stability and large magnetic moment 6 μ_B in their respective series.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.     

Laws governing the creation of electronic color centers in LiF crystals acted on by pulsed irradiation

The processes of creating and transforming electronic color centers in an LiF crystal irradiated with a nanosecond electron pulse are investigated using pulse spectrometry with nanosecond resolution for times in the range 10⁻⁸ to 10⁵ sec. It is shown that the thermally activated mechanism of forming Frenkel pairs in the 12–200 K range consists of successively creating exciton states, as the temperature rises, having different degrees of spatial separation of the electron and hole components. It is concluded that the structure of self-trapped excitons evolves as a function of temperature and time, and that this evolution commences for any alkali halide crystal with the creation of self-trapped excitons ofD _2h point symmetry at 4 K. It is established that the interaction of electronic excitations with electronic color centers changes the properties of both the electronic excitations themselves and the color centers. In a crystal containing neutral electronic centers there is a fall in the yield of self-trapped excitons and Frenkel pairs and an increase in the contribution of the radiative channel for loss of the irradiation energy by the color centers. A mechanism is proposed for exciting luminescence of electronic color centers. It is established that short-lived irradiation-induced states exist, in particular a change in the spin state or in just the energy state of a center in the irradiation field, and that the appearance of these states changes the efficiency and directivity of the charge evolution of the electronic color centers. State Architectural Building Academy, Tomsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 57–75, November, 1996.     

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states of the C₂Br radical, correlating at linear geometries with ²Σ⁺ and ²Π states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, RCC=1.2621Å, R _CBr=1.7967Å, ∠ CCBr=156.1°, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C₂F and C₂Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Σ ,Π_1/2,Π_3/2 vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5 K have been calculated for the ¹² C¹² C⁷⁹Br isotopomer, to an upper limit of 2000 cm^?1, using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.