The electronic structure of alkali metal oxides

Crystalline phase total energies, band structures, the distributions of the total and partial densities of electron states, and atomic charges were calculated for lithium, sodium, and potassium oxides, peroxides, superoxides, and ozonides using the CRYSTAL 06 and GAMESS packages in the B3LYP parameterization. For the molecular phases, the geometry was optimized and molecular orbital energies calculated. The results obtained for metal oxides were compared with the experimental photoelectron spectroscopy data and used to analyze their formation and thermal decomposition.     

Band structure and chemical bond in alkali metal carbonates

The band structure, state density, optical functions, and distribution of valence and difference density in alkali-metal carbonates are calculated within the local electron-density functional theory using the method of pseudopotential in the basis of numerical pseudoorbitals. When passing from a lithium cation to a potassium one, the character of hybridization between the crystal sublattices changes to result in an increase in the valence-band width, a decrease in the forbidden-band width, a complication of the structure of state-density spectrum, and a shift of the maxima of optical functions to the low-energy range. It is found that the electron overflow between the σ-and π-orbitals of crystallographically nonequivalent oxygen atoms can occur in different ways, hence their interaction force with the surrounding atoms is different. The role of cations in stabilization of anion chains resulting from the electron-cloud overlapping in lithium and sodium carbonates is shown. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 61–65, October, 2006.     

Band structure and optical properties of alkali metal halides

Optical spectra, photoemission spectra, and photoconductivity spectra of alkali metal halides are analyzed using energy band structure calculations and selection rules for direct and indirect transitions. The main feature of the band structure of MeN₃ (Me: Na, K, Rb, Cs) as proposed by the authors is the presence of two conductivity bands, one anionic and the other cationic in nature. A weak dispersion of the valence subband indicates that phonons may yield a significant contribution to the observed spectra. All of the optical and photoemission spectra so far reported for the metal azides may be explained on the basis of the proposed band model.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 3–7, January, 1995.     

Electronic structure of carbon nanotubes modified by alkali metal atoms

The electronic structure and parameters of the energy band structure of (n, 0)-type nanotubes modified by alkali metal atoms (Li, Na) and intercalated by potassium atoms are studied. The quantum-chemical semiempirical MNDO method and a model of the covalent cyclic cluster built in via ionic bonding are used to model infinitely long nanotubes. The electronic density of states of modified nanotubes is found. It is shown that semiconductor-metal transitions can occur in semiconductor nanotubes and that semimetal nanotubes can undergo metal-metal transitions.     

Molecular structure of alkali metal 4‐nitrobenzoates

The influence of lithium, sodium, potassium, rubidium, and cesium on the electronic system of the 4‐nitrobenzoic acid molecule was studied. The vibrational (FT‐IR, FT‐Raman) and NMR (¹H and ¹³C) spectra for 4‐nitrobenzoic acid salts of alkali metals were recorded. The assignment of vibrational spectra was done. Characteristic shifts of band wavenumbers and change in band intensities along the metal series were observed. Good correlation between the wavenumbers of the vibrational bands in the IR and Raman spectra for 4‐nitrobenzoates and ionic potential, electronegativity, atomic mass, and affinity of metals were found. The chemical shifts of protons and carbons (¹H, ¹³C NMR) in the series of studied alkali metal 4‐nitrobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by HF, B3PW91, B3LYP methods using 6‐311++G** basis set. The theoretical IR, Raman, and NMR spectra were obtained. The theoretical vibrational spectra were interpreted by means of potential energy distributions (PEDs) using VEDA 3 program. The calculated parameters were compared to experimental characteristic of studied compounds. Copyright © 2007 John Wiley & Sons, Ltd.     

Dynamic holography in alkali metal vapour

Problems of dynamic hologram recording on resonant absorption lines of alkali metal vapour are discussed. Light beams and media parameters are determined that are necessary for hologram recording with usable efficiency. The effects of thermal atomic motion and the radiative transport of excitation influence on the spatial frequency transfer function of two-level media are investigated. Results of hologram recording in vapour of Rb (780.0 nm) and Cs (852.1 nm) using low-power CW-lasers are presented. Transmission holograms in the volume media and reflection holograms near the boundary of the resonant vapour and the dielectric are compared. For transmission holograms the advantage of collinear read-out when using pure vapour in comparison with a counterpropagating read-out is shown, and this makes it possible to achieve higher values of hologram efficiency over a wide range of atomic density. It is shown that reflection hologram recording is characterized by higher resolution, as compared with hologram recordings in the volume of extended media. Problems of metal vapour hologram usage for laser parameter control are discussed. The feasibility of holograms in Cs-vapour usage as a spectral-selective real-time feedback element in a semiconductor laser external cavity is shown.     

Muon implantation in alkali metal hydrides

Zero, longitudinal and transverse field μSR measurements have been made on LiH, LiD and NaH. The primary motivation for the study was to elucidate the behaviour of the muons in the diamagnetic state and analysis of the time‐dependent zero field relaxation data suggests that negatively charged muonium, Mu^-, is formed and takes up a H^- vacancy site in these materials. Evidence is presented for a small (approximately 2%) reduction in the Mu^-–Li distance relative to the unperturbed nearest neighbour anion‐cation distances in the pure crystal lattices. This revised version was published online in August 2006 with corrections to the Cover Date.     

Theory of metastability in simple metal nanowires

Thermally induced conductance jumps of metal nanowires are modeled using stochastic Ginzburg-Landau field theories. Changes in radius are predicted to occur via the nucleation of surface kinks at the wire ends, consistent with recent electron microscopy studies. The activation rate displays nontrivial dependence on nanowire length, and undergoes first- or second-order-like transitions as a function of length. The activation barriers of the most stable structures are predicted to be universal, i.e., independent of the radius of the wire, and proportional to the square root of the surface tension. The reduction of the activation barrier under strain is also determined.     

Shape memory and pseudoelasticity in metal nanowires

Structural reorientations in metallic fcc nanowires are controlled by a combination of size, thermal energy, and the type of defects formed during inelastic deformation. By utilizing atomistic simulations, we show that certain fcc nanowires can exhibit both shape memory and pseudoelastic behavior. We also show that the formation of defect-free twins, a process related to the material stacking fault energy, nanometer size scale, and surface stresses is the mechanism that controls the ability of fcc nanowires of different materials to show a reversible transition between two crystal orientations during loading and thus shape memory and pseudoelasticity.     

Template synthesis of Y-junction metal nanowires

Template synthesis of large-scale Y-junction metal nanowires is reported. In this approach, a Y-shaped nanochannel porous anodic alumina (PAA) template is prepared by using a two-step anodization of aluminum in which the metal of interest, such as copper, is electrodeposited to form the Y-junction metal nanowires. The synthesis method presented here is simple and versatile. This method can be extended to the preparation of other Y-junction nanowires with desirable composition and shows great promise for the development of nanoelectronics. Received: 10 September 2001 / Accepted: 20 November 2001 / Published online: 23 January 2002     

Electro-chromic effects in alkali metal bronze crystals

Electric field induced switching between two distinct color states has been observed on the surfaces of some alkali metal bronze crystals. Both color states are permanent and require no sustaining voltage. Color reversal is accomplished by reversing the polarity of the applied pulse. Typically, a 50 msec switching speed is achieved with less than 5V and current densities of the order of mA.s/cm². These electrochromic effects are visually dramatic enough to make them potentially useful for a variety of reflective display applications.     

Twist mode in spherical alkali metal clusters

A remarkable orbital quadrupole magnetic resonance, so-called twist mode, is predicted in alkali metal clusters where it is represented by Ipi = 2(-) low-energy excitations of valence electrons with strong M2 transitions to the ground state. We treat the twist by both macroscopic and microscopic ways. In the latter case, the shell structure of clusters is fully exploited, which is crucial for the considered size region ( 8相似文献   

The migration of alkali metal (Na+, Li+, and K+) ions in single crystalline vanadate nanowires: Rasch-Hinrichsen resistivity

We report the synthesis of single crystalline alkali metal vanadate nanowires, Li-vanadate (Li₄V₁₀O₂₇), Na-vanadate (NaV₆O₁₅), and K-vanadate (KV₄O₁₀) and their electrical properties in a single nanowire configuration. Alkali metal vanadate nanowires were obtained by a simple thermal annealing process with vanadium hydroxides(V(OH)₃) nanoparticles containing Li⁺, Na⁺, and K⁺ ions and further the analysis of the migration of charged particles (Li⁺, Na⁺, and K⁺) in vanadate by measuring the conductivity of them. We found that their ionic conductivities can be empirically explained by the Rasch-Hinrichsen resistivity and interpreted on the basis of transition state theory. Our results thus indicate that the Li ion shows the lowest potential barrier of ionic conduction due to its small ionic size. Additionally, Na-vanadate has the lowest ion number per unit V₂O₅, resulting in increased distance to move without collision, and ultimately in low resistivity at room temperature.     

An alkali metal vapor laser amplifier

The operation of a transversely diode-pumped alkali metal vapor laser amplifier is theoretically studied. The amplifier operation is described by a rather intricate system of differential equations, which can be solved in the general case only numerically. In the case of intense incident radiation, an analytic solution is obtained which makes it possible to determine any energy characteristics of the laser amplifier and to find the optimal parameters of the active medium and pump radiation (temperature, buffer gas pressure, and intensity and width of the pump radiation spectrum).     

Lattice relaxation at alkali metal surfaces

The surface relaxation of the first interlayer spacing for both the (110) and (100) faces of alkali metals has been calculated selfconsistently using the density functional formalism and a new density matrix method which obviates the use of wavefunctions. For the (110) surfaces of all alkali metals we find no or only very small relaxation. The (100) surfaces show bigger relaxation effects and these vary from 3.5% inward for Li to 1% outward for Cs. These findings are consistent with general trends found in LEED or Ion scattering studies. Force constants for the movement of the last atomic layer are also determined.     

Ionic conductivity of alkali metal chloroaluminates

The electrical conductivity of three alkali metal chlorluminates has been investigated from room temperature to above the melting point. Ionic conductivities at 25°C are 1.2 × 10^?6, 3.5 × 10^?7 and 3.2 × 10^?9omh^?1 cm^?1, and activation enthalpies are 0.47, 0.46 and 0.53 eV for LiAlCl₄, NaAlCl₄ and KAlCl₄.     

Spectra of alkali metal carbonates in the 4–11-eV region and their electronic structure

Journal of Applied Spectroscopy -