Influence of a magnetic field on the electronic Raman response in high-Tc cuprates

The effect of a magnetic field parallel to the CuO₂ plane on the Raman spectra is investigated based on the Slave–Boson approach to the t − t′ − J model with a Zeeman field and the random-phase approximation. We find that the Raman spectra intensities in the superconducting (SC) state are suppressed for both the B_1g and the B_2g channels with a slight shift of the peaks position toward lower frequency in the B_1g channel and a negligible shift in the B_2g channel due to the Zeeman splitting. There is a field-induced peak and dip structure at low energy response in the B_2g channel at very low temperature. While rising temperature has a similar effect in reducing the Raman response peak in the superconducting (SC) state, it smears out the field-induced peak and dip structure in the B_2g channel. We compare these results with experiments and give explanations based on the field-induced changes of the density of the superconducting condensate, the momentum distribution of the quasiparticle energy and the scattering rate.     

Vapour phase M4,5N4,5N4,5 Auger electron spectra of antimony and tellurium

High resolution M_4,5N_4,5N_4,5 Auger electron spectra from Sb₄ and Te₂ vapours have been measured using electron impact excitation. The spectra have been decomposed into line components and relative intensities and energies of the components are compared with calculated intensities and energies. The calculations have been done for these molecular samples using the free-atom calculation model involving initially filled shells. The calculations have been treated in the mixed coupling scheme using jj coupling for initial state and intermediate coupling for the final state. The experimental results agree well with the calculated values, indicating that the molecular effects on the relative intensities and energies are very small for these core level transitions. The clear molecular effects are found in the broadening of lines and in the kinetic energy shifts due to extra-atomic relaxation effects.     

One-electron spectrum of Yb+: Relativistic energies,transition probabilities and dipole polarizability

Calculations are reported of relativistic ionization energies and transition probabilities in the one-electron spectrum of singly-ionized ytterbium. The relativistic model potential approach used takes into account both valence-core electron exchange and correlation. The influence of polarization of the core by valence electrons on ionization energies and transition probabilities has been studied. Strong cancellation effects have been found for higher transitions of the principal series; these affect both transition probabilities and relative line strengths. The energies are predicted for some states which have not yet been experimentally localized. The static dipole polarizability for Yb⁺ is estimated to be 48.18 g₀³ from computed oscillator strengths; this estimate is compared with lower bounds determined from experimental data.     

Electronic structure of the F-center in CaO and MgO

The energy levels and wave functions of the F-center in CaO and MgO have been calculated as function of the A_1g and E_g displacements of the nearest neighbor ions of the oxygen vacancy. In CaO, the calculated level scheme partially supports the interpretation of published experimental data on the luminescence bands but there are significant discrepancies. The localization of the wave function of the ³T_1u state is rapidly varying function of the A_1g lattice distortion. The present calculations give a Jahn-Teller splitting of this state of between 0.15 and 0.2 eV.     

First-principles calculation of the energy of compressed calcium

The energy of a calcium crystal with a simple cubic lattice as a function of the ratio (t/U) between two internal parameters of the Hubbard model has been calculated using the Hubbard model for the s bands, equations of motion, and direct algebraic method. The electronic spectra have been calculated for the 4s band of the crystal in two principal symmetry directions of the first Brillouin zone. The calculations have been performed at temperatures T ₁ = 0 K and T ₂ = 1000 K. All calculations have been carried out for different interaction energies U of s electrons, one angle, and their different concentrations n in the range 0 ≤ n ≤ 2. The calculations have demonstrated that the dependences of the energy and electronic spectra in this compressed state are very smooth. The occupation of the Ca 4s band is in good agreement with the results of the pioneering calculations of compressed Ca (and a number of other metals), which were carried out by Gandel’man and his colleagues in the Wigner-Seitz spherical cell approximation. It has been shown that the performed analysis accurately reproduces the data obtained on the superconductivity in terms of the Bardeen-Cooper-Schrieffer theory if the 4s band is half-occupied.     

Inclusion of relativistic effects into ZDO methods. VI. Stability or Jahn-Teller instability of octahedral gold and copper complexes

Quasirelativstic and relativistic (four-component) versions of the CNDO (Complete Neglect of Differential Overlap) methods have been used in studying the electronic structure of octahedral²[CuF₆]^4–,²[AuF₆]^4– complexes and ^m [Cu₆] ^q , ^m [Au₆] ^q and ^m [Au₆(PH₃)₆] ^q clusters for various charges,q, and spin multiplicities,m. A strong spin-orbit splitting of levels t_1u in [Au₆]²⁺ cluster removes the degeneracy of the ground electronic state³T_1g into a nondegenerate state so that the Jahn-Teller instability disappears as a consequence of the relativistic effect. The phosphine ligands change the redox stability of the cluster as the orbital energies are shifted to higher values. On the contrary, the spin-orbit splitting of completely filled t_2u levels in [AuF₆]^4– is irrelevant since the degeneracy of the ground electronic state²E_g (_8g in the double group notation) remains unchanged. Consequently the Jahn-Teller instability of the octahedral geometry exists and thus a considerable tetragonal distortion appears.Part V: J. Quantum Chem.36 (1989) 727.     

Electronic structure of Cr1−δS (δ=0, 0.17) with NiAs-type crystal structure

Valence-band and conduction-band the electronic structure of the CrS (δ=0) and Cr₅S₆ (δ=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. The bandwidth of the valence bands of Cr₅S₆ (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds concerning shapes as well as binding energies. The Cr 3d (t_2g) exchange splitting energies of CrS and Cr₅S₆ are determined to be 3.9 and 3.3 eV, respectively.     

Wavelength modulated absorption in SiC

Wavelength modulated absorption spectra of the free excitons in 6H, 15R and 3C SiC have been measured. The spin-orbit splitting of the valence bands of the uniaxial and cubic polytypes are found to be 7 and 10 meV respectively. Using a new value for the exciton binding energy of 27 meV, an improved value of the fundamental gap of cubic SiC, E_g = 2.417 eV, is derived. Due to the small spin-orbit splitting, the valence bands are highly non-parabolic at low energies.     

Level splitting in semimagnetic semiconductors under spin-magnetophonon resonance conditions

The splitting of electronic levels in quantum wells of semimagnetic semiconductors typically characterized by large effective g factors is analyzed theoretically. They are found to be capable of supporting resonance, provided the Zeeman spin-level splitting is equal to the energy of the longitudinal optical phonon ?ω_‖. The resonance condition can be written as ?ω_‖ = gμ_B B. This condition can be satisfied by choosing the magnetic field Bsuch that the sum of the energies of the lowest spin level and the optical phonon coincides with the energy of the highest level. It is shown that these two degenerate energy levels should experience mutual repulsion. The magnitude of the corresponding splitting depends on both the electron-phonon and spin-orbit interactions in semiconductors; moreover, it turns out substantially lower than the Zeeman energy gμ_B B. Resonant passage of light through and its reflection from a quantum well are considered as one of possible ways to observe this energy level splitting.     

The effects of crystal field on Nd(su3+) in the laser host YVO(in4)

The behavior of Nd³⁺ in the laser host yttrium orthovanadate, YVO₄, has been investigated with respect to its absorption spectra By taking into consideration intermediate coupling, a new set of crystal field parameters is obtained which gives a lower rms deviation between observed and calculated energies for 25 of the 26 levels of the ⁴I term than that reported earlier using a pure Russell-Saunders basis. The computed g-factors are also in good accord with resonance results Vanous quantities including the nuclear hyperfine parameters have been calculated Nuclear properties which depend on the crystal field are predicted for both the isotopes of Nd     

The large-amplitude motions in quasi-symmetric top molecules with internal C3v rotors: Interpretation of the low frequency Raman spectrum of disiloxane

The vibration-torsion-rotation Hamiltonian developed previously has been used to study the skeletal bending-torsion-rotation energy levels of disiloxane. The zeroth-order skeletal bending-torsion-rotation Hamiltonian for a molecule of this type is presented. The symmetry classification of the molecular wavefunctions and energy levels as well as infrared and Raman selection rules are considered. The energies of the skeletal bending-torsional-rotational states have been calculated and these results are used to interpret the low frequency Raman spectra of gaseous disiloxane-d₀ and disiloxane-d₆. It is shown that the treatment presented enables one to properly interpret these spectra. The results are compared to those obtained with other more approximate Hamiltonians.     

Precise measurement of the KLL and KLX Auger spectra of cadmium from the EC-decay of 111In

The KLL and KLX Auger spectra of Cd from the EC-decay of ¹¹¹In have been analyzed with the 7 eV instrumental resolution using a combined electrostatic spectrometer and a source prepared by a modified Langmuir–Blodgett method. Energies and relative intensities of all the nine well resolved KLL lines have been precisely determined. While the latter quantities were found to be in very good agreement with the relativistic intermediate coupling calculations, the former ones deviate from results of the widely used semi-empirical calculations especially in the case of the absolute energies. The predicted strong influence of the relativistic effects on the KL₁L₂(³P₀) transition intensity has been proved. Most of the main KLX Auger lines have been well separated and their complex structures have been observed. Accurate energies and intensities obtained for these lines have been compared with results of calculations. The intermediate coupling splitting of the KL₂L₂ and KL₃L₃ lines have been revealed. The KLX/KLL, KLN(O)/KLM, and KXY/KLL group intensity ratios have also been determined. A conclusion is made that further finer theoretical investigation on the complex interaction mechanism for two inner-shell vacancies is still very much needed.     

Selective laser spectroscopy of Mn4+-Mn4+ pair centers in SrTiO3 crystal

Zero-phonon lines of a pair center of Mn⁴⁺ ions are observed in the luminescence and luminescence-excitation spectra of SrTiO₃:Mn crystal. Based on the experimental data, the energy-level structure of the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and excited state ∣⁴ A _2g ,² E _g 〉 of the Mn⁴⁺-Mn⁴⁺ pair center is constructed. It is shown that the exchange interaction in the ground state of the Mn⁴⁺-Mn⁴⁺ pair is antiferromagnetic. Energies of the levels are calculated assuming that the pair is formed by Mn⁴⁺ ions occupying neighboring octahedral positions of Ti⁴⁺ ions along the [110] axis. Experimental values of the exchange integral in the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and energies of spin multiplets in the excited state ∣⁴ A _2g ,² E _g 〉 agree well with calculation of the exchange interaction carried out within the framework of the channel model with the parameters J _ξη = 32 cm^4-1 and J _ζζ = ?45.5 cm^4-1. Experimental data and calculations unambiguously demonstrate that zero-phonon lines in the luminescence and luminescence-excitation spectra have magnetic-dipole nature.     

Tight-binding calculation of the optical conductivity in NaxCoO2

Optical conductivity in Na_xCoO₂ is calculated with tight binding approximation. The calculated gross features agree with the experimental findings. Interband transitions between nearly degenerate t_2g bands bring about absorption in the mid-infrared and near infrared regions. Structures observed at higher energies are also quite well reproduced with the present calculation. Possible effects of electron correlation are also briefly discussed.     

Particle Production in Non-equilibrium Thermodynamic States in Nucleus-Nucleus Collisions

The formation of nonequilibrium thermodynamic system is assumed during the collision of relativistic heavy ions with target nuclei. A simple classical solution of the Boltzmann equation is found and compared with the spectra of particles produced in the Ne-U²³⁸ reaction at lab. energies of 250 and 400 MeV per nucleon. The model contains only one fitting parameter t_c which is the time required by the system to reach the equilibrium state.     

Fully relativistic calculations of the L2,3-edge XANES spectra for vanadium oxides

Fully relativistic multielectron method based on the numerical solution of the Dirac equation was used to calculate the L_2,3-edge X-ray absorption near edge structure (XANES) spectra of VO₂, V₂O₃, and V₂O₅ crystals. The key-points of the method are: i) usage of the molecular orbitals (MO); ii) absence of any fitting parameters; iii) wide area of application: to any ion in any symmetry; iv) possibility of numerical analysis of the MO composition. The calculated spectra are in a satisfactory agreement with experimental data available in the literature, including the absolute values of the transitions energy, the shape of the absorption bands, and polarization dependence. The assignment of the absorption bands in terms of the electronic configurations was done. The structure of the absorption bands is attributed to the splitting of the vanadium p- and d-orbitals; the magnitude of this splitting is estimated from the spectra. Covalency effects were considered for all hosts; it was shown that the contribution of the oxygen wave functions increases with increasing the vanadium oxidation state. Dependence of the relative positions of the vanadium 3d and oxygen 2p levels and energies of the “ligand–metal” charge transfer transitions on the vanadium oxidation state was analysed.     

Valence band contributions to photoluminescence excitation spectra of tightly bound holes in zincblende semiconductors

Photoluminescence excitation (PLE) spectra of deep acceptor states in ZnSe, for example the Cu-related luminescence band at ≈1.95 eV, contain a prominent excitation band at ≈3.25 eV. This band lies above the structure marking the lowest direct E_O band gap E_g by the spin-orbit splitting energy Δ of the valence bands at Γ. The higher energy feature is either absent or greatly de-emphasised in the PLE spectra of shallow acceptor states in ZnSe and of the oxygen iso-electronic trap in ZnTe, where the electron rather than the hole is tightly bound. However, a significant PLE component at E_g + Δ is observed for deep acceptor-like states in ZnTe, where Δ is ≈0.95 eV. Efficient PLE at E + Δ for luminescence from deep acceptor-like states is shown to be consistent with the extended wave-vector contributions to the bound state wave-functions of holes of binding energies ≈Δ.     

Phase transitions at high pressure in the fullerene C60 molecular donor-acceptor complex {Hg(dedtc)2}2 · C60

Raman spectra of crystals of the molecular fullerene C₆₀ donor-acceptor complex {Hg(dedtc)₂}₂ · C₆₀ (fullerene with mercury diethyldithiocarbamate) have been measured at a pressure up to 8.4 GPa and at room temperature. A phase transition has been revealed in the pressure range of 1.2–2.0 GPa, which is accompanied by a splitting of the degenerate intramolecular phonon modes H _g (1)-H _g (4) and H _g (7)-H _g (8), as well as by a softening of the H _g (2) mode of the fullerene C₆₀. As the pressure further increases to the maximum value, the intensity of the bands varies smoothly. A decrease in the pressure leads to the reverse transition to the initial state at 1.2 GPa. The splitting of the degenerate modes H _g (1)-H _g (8) and the softening of the H _g (2) modes resemble their behavior in the formation of dimers in fullerite crystals and indicate the possible formation of dimers in two-dimensional fullerene layers under hydrostatic compression of the {Hg(dedtc)₂}₂ · C₆₀ complex.     

The methane ν1(a1) vibrational state rotational structure obtained from high-resolution CARS-spectra of the Q-branch

The gaseous methane ν₁(a₁), Q-branch coherent anti-Stokes Raman scattering (CARS) spectra have been investigated at a resolution of 0.002 cm^?1. A complex rotational structure of the resolved Q-branch has been experimentally observed. This structure can be ascribed to strong tetrahedral splitting of the rotational levels of the upper vibrational state, which possibly occurs due to Fermi resonance between the ν₁(a₁) and 2ν₂(a₁) vibrational energy levels which are close to each other. An assignment of the observed spectral lines has been made, yielding the rotational constants B, D, and D_t for the ν₁(a₁) vibrational state of the methane molecule. The absolute Raman frequency ν₁ of the purely vibrational transition has been found.