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.     

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.     

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.     

Ionization energies of liquids from energy distribution,quantum yield and second derivative curves

The energies of the lowest ionization band of eight liquids of low vapor pressure are determined from energy distribution curves (EDC), quantum yield spectra (collected electrons per incident photon as a function of photon energy), and second derivative curves (SDC) of retarding potential curves. Threshold energies from EDCs and quantum yield spectra agree if one takes into account a 0.15 e V shift caused by the spectrometer's rather low resolution and a small difference (0.15 eV or less) resulting from the use of approximate extrapolation methods. Threshold energies from EDCs and SDCs agree to within 0.1 eV after correction for the half-width of the high-energy branch of SDCs. Multiple ionization bands are exhibited by the SDCs of some of the liquids, and the observed splittings agree well with the results from gas-phase UPS spectra. A new spectrometer for the measurement of EDCs of liquids is described. The liquids studied are 6-chloro-1-hexanol, 2-ethyl-1-hexanol, ethylene cyanohydrin, ethylene glycol, 1,5-pentanediol, tetraglyme, triethylene glycol and tetraethylene glycol.     

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.     

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.     

Exciton spectra, valence band splitting, and energy band structure of CuGaXIn1−XS2 and CuGaXIn1−XSe2 crystals

Exciton spectra are studied in CuGa_XIn_1−XS₂ solid solutions by means of photoreflectivity and wavelength modulation spectroscopy at liquid nitrogen temperature. The exciton parameters, dielectric constants, and free carrier effective masses are deduced from experimental spectra by calculations in the framework of a model taking into account the spatial dispersion and the presence of a dead-layer. The crystal field and spin orbit valence band splitting is calculated as a function of X taking into account the energy position of excitonic lines. The energy band structure of CuGa_XIn_1−XS₂ and CuGa_XIn_1−XSe₂ compounds is derived from optical spectra at photon energies higher than the fundamental band gap. The energies of optical transitions are tabulated for X values from 0 to 1.     

First-principles investigation of the surface structures of Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces

Multilayer relaxation at high-index Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces was determined by the first-principles pseudopotential plane wave (PPPW) method. For those surfaces that have n and n−1 atom-rows in terrace and subterrace, respectively, the topmost 2n−2 interlayer spacings contract, while the 2n−1st interlayer spacing expands. There is no similar rule found for the relaxations parallel to the surfaces. Compared with the bulk terminated structure, a thin compact layer, which consisted of the topmost 2n−1 atom layers and separated slightly from the underneath atom layers, makes the surface more flat after relaxation. The bond-lengths between the step edge (first layer) atom and its nearest-neighbors do not depend on the surface termination, but only on the local coordination.     

Structural investigations of the xTeO2-(1−x)GeO2 (x=0, 0.2, 0.4, 0.6, 0.8 and 1) tellurite glasses: A composition dependent Raman spectroscopic study

Raman spectra of xTeO₂-(1−x)GeO₂ (x=0, 0.2, 0.4, 0.6, 0.8 and 1) germanium tellurite glasses were measured and analyzed in an effort to follow the structural changes caused by mixing two typical glass formers. Systematic Raman intensity measurements have been performed in an effort to elucidate the composition induced structural changes and a possible mechanism accounting for these changes was proposed. The network structure of the glass is characterized by TeO₄ trigonal bipyramid mixed with TeO₃ trigonal pyramid units, while GeO₄ tetrahedral units are also present. Changing the GeO₂ content results in the conversion of the TeO₄ units to TeO₃ units with a neutral doubly bridged oxygen atom, while the existence of charged terminal oxygen atoms is questionable. The measured relative Raman intensities are semi-quantitatively correlated to the transformation of the TeO₄ trigonal bipyramid to TeO₃ trigonal pyramids.     

Analytical potential energy function for the electronic states 2^∏1/2 and 2^∏3/2 of O^x2 （x=＋1, -1）

The splitting of potential energy levels for ground state X^2∏g of O^x2 （x = ＋1,-1） under spin-orbit coupling （SOC） has been calculated by using the spin-orbit （SO） multi-configuration quasi-degenerate perturbation theory （SO-MCQDPT）. Their Murrell-Sorbie （M S） potential functions are gained, and then the spectroscopic constants for electronic states 2^∏1/2 and 2^∏3/2 are derived from the M S function. The vertical excitation energies for O^x2 （x = ＋1,-1） are v[O2＋1^（2∏3/2→X^2∏1/2）] =195.652cm^-1, and v[O2^-1（2^∏1/2 →X^2∏3/2）] =182.568cm^-1, respectively. All the spectroscopic data for electronic states 2^∏1/2 and 2^∏3/2 are given for the first time.     

First-principles calculations of the effect of Ge content on the electronic,mechanical and acoustic properties of Li17Si4-xGex

The electronic, mechanical and acoustic properties of Li₁₇Si_4-xGe_x (x = 0, 2.3, 3.08, 3.53, and 4) have been investigated by using first-principles calculations based on the density functional theory (DFT). The research shows that the bulk modulus B, Young's modulus E, shear modulus G, and hardness H_v gradually decrease with the increasing Ge content. Li₁₇Si_4-xGe_x have the brittle nature from the analysis of B/G ratio and Cauchy pressure. The maximum Young's moduli are all along [1 1 0] plane, and the sequence of degree of anisotropic property is Li₁₇Ge₄ > Li₁₇Si_0.48Ge_3.52 > Li₁₇Si_0.92Ge_3.08 > Li₁₇Si_1.7Ge_2.3 > Li₁₇Si₄. The analysis of acoustic velocity shows that all the sound velocities decrease with the increasing Ge content for Li₁₇Si_4-xGe_x (x = 0, 2.3, 3.08, 3.53, and 4), and the longitudinal wave along [111] direction is fastest for the studied compounds. Debye temperature Θ_D, v_t and v_l decrease with the increasing Ge content. The minimum thermal conductivity decreases with the increasing Ge content, and Li₁₇Si_4-xGe_x have low thermal conductivities and are not potential thermal conductors. The analysis of electronic properties indicates that Li₁₇Si_4-xGe_x have the metal nature and anisotropic electrical conductivity. The electric conduction is improved with the increasing Ge content.