Magnetic circular dichroism of band-edge exciton absorptions in PbI2

The linear Zeeman behaviour of the n = 1, 2 and 3 exciton absorptions near 20000 cm^-1 in PbI₂ single crystals was determined from measurements of the magnetic circular dichroism. The similarity of the g-value (+ 1.5 ± 0.5) for each of the n = 1, 2 and 3 lines supports the hydrogenic model. Any quadratic shifts of the n ? 2 levels were < 10 cm^-1 in an applied magnetic field of 21 T.     

On the photoelectron spectra of UO2

The Mg Kα and He(II) photoelectron spectra of polycrystalline UO₂ have been recorded. Particular care was taken to prepare a sample surface which was both representative of the bulk and as close to the ideal stoichiometry as possible. The origin of satellite structure in core-level spectra is discussed with the aid of a multi-configuration Dirac—Fock atomic calculation.     

Electronic structure of the valence bands of SnCl2 and SnBr2 studied by ultraviolet photoelectron spectroscopy

A photoelectron study of the outermost bands of solid-phase SnCl₂ and SnBr₂ using 40.81 eV photons is reported. The main features of the spectra are successfully interpreted in terms of molecular orbital theory for the appropriate isolated molecules.     

Band-edge photoluminescence of PbI2

Photoluminescence spectra of the hexagonal layered semiconductor PbI₂ have been measured at 4.2°K on various single crystalline specimens. They are interpreted in relation with the anisotropic polariton model. The emitted radiation is assumed to originate from free and bound exciton recombination, with and without phonon emission. A peak polarized E ∥ c about 4 meV above the excitonic line is related to the extraordinary polariton mode.     

X-ray and UV photoelectron spectra of the oxides NbO2, MoO2 and RuO2

HeI and Mg Kα_1,2 valence band photoelectron spectra of polycrystalline samples of NbO₂, MoO₂ and RuO₂ are reported. A marked increase is observed in the intensity of the metal 4d structure, relative to that due to oxygen 2p electrons, on changing from X-ray to UV excitation. The superior resolution of the 4d signals in the HeI spectra reveals the presence of the Fermi edge in the metallic oxides MoO₂ and RuO₂. In addition, the HeI spectrum of MoO₂ shows a splitting of the metal 4d signal, confirming established ideas concerning the electronic structure of such materials.     

Electronic structure studies of the spinel CoFe2O4 by X-ray photoelectron spectroscopy

The spinel CoFe₂O₄ has been synthesized by combustion reaction technique. X-ray photoelectron spectroscopy shows that samples are near-stoichiometric, and that the specimen surface both in the powder and bulk sample is most typically represented by the formula (Co_0.4Fe_0.6)[Co_0.6Fe_1.4]O₄, where cations in parentheses occupy tetrahedral sites and those within square brackets in octahedral sites. The results demonstrate that most of the iron ions are trivalent, but some Fe²⁺ may be present in the powder sample. The Co 2p_3/2 peak in powder sample composed three peaks with relative intensity of 45%, 40% and 15%, attributes to Co²⁺ in octahedral sites, tetrahedral sites and Co³⁺ in octahedral sites. The O 1s spectrum of the bulk sample is composed of two peaks: the main lattice peak at 529.90 eV, and a component at 531.53 eV, which is believed to be intrinsic to the sample surface. However, the vanishing of the O 1s shoulder peak of the powder specimen shows significant signs of decomposition.     

The lattice polarizability of PbI2

We have measured the far-i.r. reflectivity spectrum of the layer crystal PbI₂ for the in-plane polarization. A strong reststrahlen band is observed, with TO and LO phonon frequencies located at 52 and 108 cm^?1. The large lattice contribution accounts for three-quarters of the low-frequency dielectric constant of 26. The deduced infrared effective charge and electronic polarizability of PbI₂ indicates that the intralayer bonding is closely related to the chemical bonding in the IV–VI rocksalt-structure crystals.     

Electron energy loss spectra and X-ray photoelectron spectra of Ca2V2O7

We have measured the electron energy loss spectra of Ca₂V₂O₇ in the reflexion mode, at incident energies between 200 and 2400 eV, and the X-ray photoelectron spectra excited by Al K α radiation. The abundant loss structures observed can be correlated with the possible interband transitions, collective oscillations, and excitation of O2s and V3p electrons within the V₂O₇^4- ion. The gap width and molecular orbital (MO) spread (or splitting) is about l eV larger in the V₂O₇^4- ion than in its component VO₄^3- ion. Excitation of O2s states, which may occur together with some MO over-gap transitions, displaces the collective oscillations about 7 eV towards lower energies. Deeper V3p electrons are excited with a maximum energy loss some 7 eV above their binding energy. Cross transitions from Ca3p levels into some empty states of the V₂O₇^4- ion, or direct transitions to available states of the Ca²⁺ ion could not be unambiguously identified. The energy dependence of the excitation cross section and of the electron penetration depth results in a significant variation of the relative intensity of various losses over the investigated energy range.     

Electronic structure of AgNbO3 and NaNbO3 studied by X-ray photoelectron spectroscopy

The XPS examinations of the AgNbO₃ and NaNbO₃ single crystals and ceramics allowed estimate their average composition as Ag_1.1Nb_0.9O₃ and Na_1.2Nb_0.9O_2.9. The valence bands of the AgNbO₃ compound, formed mainly of the Nb 4d, Ag 4d and O 2p states, show an energy gap about 3 eV while for the NaNbO₃ compound consist of the O 2p states hybridized with the Nb 3d states and show an energy gap about 4 eV. The chemical shifts of these compounds suggest a mixed ionic and covalent character of the bonds. The broadening of the core level lines of AgNbO₃ suggests a stronger structural disorder in comparison with NaNbO₃ compound.     

Low temperature thermal properties of PbI2

The heat capacity and thermal conductivity of a large (56.5 g) crystal of PbI₂ have been measured in the temperature region 0.5 < T < 3.9°K. Analysis of the heat capacity data yields a value of the limiting apparent Debye characteristic temperature θ₀^c = 99.4 (±0.3)°K, which corresponds to an average lattice wave velocity of 1.151 (±0.005) × 10⁵ cm sec^?1. It is consistent with a wave velocity estimated from neutron scattering experiments, but not with one determined from Brillouin spectra. The heat capacity data also show that dispersion of the low frequency waves is not unusual, as might have been expected for a layer-type crystal. The apparent thermal conduction is found to be surprisingly small in the crystal.     

Electronic structure of ErH2

A band structure study reveals that in contrast to the pure rare earth metal, the Fermi level of the dihydride falls near the bottom of the 5d band, in a region of low density of states; consequences on Fermi surface geometry, magnetic properties and resistivity are suggested. Below the metal d states lie two overlapping metal-hydrogen bands, in agreement with Weaver's photoemission data and Switendick's result on YH₂.     

Electronic structure of TiH2

The electronic structure of TiH₂ has been studied using the augmented-plane-wave method and the LCAO interpolation. The density of states and its orbital components show that the conduction band is Ti d-like and that the valence band is largely derived from the hydrogen orbitals with small Ti 3d hybridization. The electronic charges on the hydrogen atom are ～ 1.5 as compared to 1.6–1.7 of the rare-earth metal hydrides.     

A theoretical study of photoelectron spectra of NbO2, MoO2 and RuO2 by cluster models

DV-Xα calculations have been applied to various small clusters of rutile-family dioxides (NbO₂, MoO₂ RuO₂). It appears that by taking into consideration the potential due to the atomic charges, the density, the ionization cross sections of the energy levels, and by summing the density of states (DOS) of the two different clusters representing surface structures, computations on even small clusters provide information which compares well with the experimental XPS spectra.     

Cooperative fluorescence by excitonic resonant pumping in PbI2 and HgI2

The behaviour of the cooperative emission from PbI₂ and HgI₂ at 80 K has been studied at high exciton density by means of a tunable high intensity dye laser pumping. From a comparative analysis of the observed M and S stimulated emission lines from PbI₂ and HgI₂ we find that they strongly depend in two different ways on the pumping photon energy. Then, it is also possible to conclude that exciton-exciton and exciton-electron inelastic scattering are responsible for stimulated emission in PbI₂ and HgI₂ respectively.     

Faraday rotation and surface excitons in PbI2

The fine structure of exciton spectrum in thin films of PbI₂ on NaCl substrate is investigated with the help of the Faraday rotation. The narrow negative peaks B and B' situated at 2.535 and 2.528 eV (90°K) correspond, as it is shown, to the surface excitons which are excited in the molecular layers of PbI₂ bordering with vacuum and NaCl surface.     

Electronic structure and bonding in ThO2 and UO2

Electron energy levels and charge densities for ThO₂ and UO₂ are calculated in a molecular cluster approximation, using spin unrestricted Hartree-Fock-Slater and relativistic Dirac-Slater models. Results compare favorably with X-ray photoelectron spectra and reveal similarities in chemical bonding with rare earth oxides.     

Autlerben Townes splitting in photoelectron spectra of K2 molecule

We investigate Autler-Townes splitting in the photoelectron spectra of K₂ molecule driven by pump-probe pulses via employing the time-dependent wave packet approach. It is found that the magnitude of Aulter-Townes splitting varies with the wavelength of the intense laser pulse. In particular, the phenomenon of Aulter-Townes splitting vanishes for the far-off resonance of the pump pulse. Also, the split peaks of Autler-Townes in the case of resonant pump pulse give us an approach to directly obtaining the transition dipole moment of a molecule.     

Inter-polytype conversion and layer-layer coupling in PbI2

The occurrence of a thermally-induced 2H → 4H inter-polytype conversion in PbI₂ has been observed via the appearance, in Raman scattering, of a shear-motion rigid-layer line at 14 cm^-1 and a Davydov splitting of an intra-layer line. Analysis of these data has yielded a comparison of the layer-layer coupling strength in PbI₂ with that in other layer crystals, as well as an estimate of the stiffness of the iodine-iodine interlayer bond.