The electronic structure of the S8 molecule

The UV and X-ray photoelectron spectra of the S₈ molecule are presented together with an SCF-Xα-SW calculation of the electronic structure. The calculated optical transition energies are also presented and compared with the experimental UV absorption spectrum.     

Semiconducting properties of CuIn5S8 single crystals II. Near infrared absorption

Near infrared absorption spectra of n-type CuIn₅S₈ single crystals were measured. Two structures were found in the spectra in the photon energy range from ?ω ? 0.3 eV?1.2 eV. One of them is the free carrier absorption below 0.6 eV in which the absorption coefficient increases as the third power of the wavelength. It was found that this absorption was associated with the multiple scattering mechanisms. Another structure seems, from its temperature and carrier-concentration dependences, to be associated with an absorption due to a transition from a lower lying conduction band to an upper one.     

Superconductivity in the RexMo6S8

The rare earth molybdenum sulfides RE_xMo₆S₈ (RE = rare earth) have been synthesized and are found to be superconducting with a few exceptions. This result, which is surprising in view of the high concentration of magnetic ions, is correlated with the particular structure of these compounds based on on units of Mo₆S₈.     

Photoelectron and electronic absorption spectra of SCl2, S2Cl2, S2Br2 and (CH3)2S2

Photoelectron and electronic absorption spectra of SCl₂, S₂Cl₂, S₂Br₂, and (CH₃)₂S₂ have been measured and analyzed. Quantum chemical calculations (CNDO/ 2 and MWH (Mulliken-Wolfsberg-Helmholtz) have been carried out and the electronic structures have been described in terms of molecular orbital theory. The variation in differential photoionization cross-section as a function of incident photon energy and results of MO computations are used to identify ionization bands and assign ground state MO configurations. Suggested ground state electronic structures coupled with computed virtual MO's are used to interpret the visible and near-ultraviolet electronic absorption spectra. The low energy excited states are described as molecular states followed by the initial members of Rydberg series. Calculated oscillator strengths for molecular transitions are in good agreement with those observed experimentally. Quantum defects, δ, for the Rydberg states have been calculated from the Rydberg equation using the adiabatic first ionization potential.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

Electronic structure and chemical bonding of phosphorus-contained sulfides InPS4, TI3PS4, and Sn2P2S6

The electronic structure of phosphorus-contained sulfides InPS₄, Tl₃PS₄, and Sn₂P₂S₆ was investigated experimentally with X-ray spectroscopy and theoretically by quantum mechanical calculations. The partial densities of electron states calculated with the ab initio multiple scattering FEFF8 code correspond well to their experimental analogues—the X-ray K- and L_2,3-spectra of sulfur and phosphorus. The good agreement between theory and experiment was also achieved for K-absorption spectra of S and P in the investigated sulfides. In spite of the difference in the crystallographic structure of InPS₄, TI₃PS₄, and Sn₂P₂S₆ that influence the form of K-absorption spectra, the electronic structure of their valence bands are rather similar. This is due to the strong interaction of the P and S atoms, which are the nearest neighbors in the compounds studied. The electron densities of p- and s-states of phosphorus are shifted by about 3 eV to lower energies in comparison to the analogous electron states of sulfur. This is connected with the greater electro-negativity of sulfur, and is confirmed by the calculated electron charge transfer from P to S.     

Bi2Sr2CaCu2O8单晶a-b平面热电势率的各向异性

测量了Bi₂Sr₂CaCu₂O₈单晶a方向的热电势率S_a和b方向的热电势率S_b与温度T的关系,发现在a-b平面内热电势率存在各向异性。认为S_a与S_b的差异来源于b方向的调制结构,并用扩散热电势率S_d,声子曳引热电势率S_g和相关跳跃热电势率S_h三种贡献,对实验结果进行了 关键词：     

Photoelectron spectra of As4S3, P4S3, P4Se3 and As4O6

The He(I) UV photoelectron spectra of As₄S₃, P₄S₃, P₄Se₃ and As₄O₆ are reported in this paper. The spectra of As₄S₃ and the isostructural molecules P₄S₃ and P₄Se₃ comprise seven broad but clearly defined peaks, whilst the spectrum of As₄O₆ consists of six peaks and two shoulders. By comparing the spectra with one another and with the photoelectron spectra of other arsenic and phosphorus compounds, the character and symmetry species of the highest-energy occupied molecular orbitals of the molecules have been assigned.     

Low temperature structural distortion in the high Tc Chevrel-phase superconductors PbMo6S8 and SnMo6S8

High-resolution powder neutron diffraction data reveal that, at temperatures below 100 K, oxygen-free, high-T_c samples of PbMo₆S₈ and SnMo₆S₈ exhibit a small structural distortion from the R$\text{3}$ rhombohedral space group. The data cannot be refined in a simple P$\text{1}$ triclinic space group as previously reported for EuMo₆S₈ and BaMo₆S₈. Thus, a supercell ordering is suggested.     

Raman spectra and structure of As40−xS60Ix glasses

The Raman spectra of bulk As_40?xS₆₀I_x glasses with 0?x?20 have been studied. The obtained spectra can be successfully explained assuming the structure of these glasses to be composed of As₂S_3.45 polymer network matrix with dissolved AsBr₃ and S₈ molecules.     

Photoemission study of the density of valence states of amorphous As2S3 and Sb2S3

The densities of valence states of amorphous As₂S₃ and Sb₂S₃ have been investigated by means of X-ray photoemission and ultraviolet photoemission spectroscopy. The spectra are interpreted on the basis of existing band structure calculations.     

Lattice instability in the non-superconducting compound EuMo6S8

We have performed electrical resistivity and specific heat measurements on bulk Eu_1.1Mo₆S₈ together with low-temperature X-ray powder diffractometry. These investigations revealed a structural phase transition (occuring at 109 K) from the room-temperature rhombohedral structure to a low-temperature triclinic distorted structure in which the compound exhibits a non-metallic behavior.     

Raman spectra of As4S4 polymorphs: Structural implications for amorphous As2S3 films

Raman-scattering spectra of α-As₄S₄ and β-As₄S₄ have been determined at 300 and 10 K. Although similar in overall aspect, the spectral signatures of the two polymorphs are clearly distinct. We have made a careful comparison of these first-order crystal line spectra to the sharp features reported in the Raman spectra of freshly-deposited films of amorphous As₂S₃. Prior proposals for the presence of As₄S₄ molecules in the unannealed films are supported by these comparisons, but recent contentions that actual microcrystals of β-As₄S₄ are present in the as-deposited material are clearly contradicted by the absence of any of the lattice-phonon lines which are prominent in the crystals at frequencies below 70 cm^-1.     

MAGNETIC FIELD EFFECT OF THE EUROPIUM a8S7/2-z6P7/2 LINES

The magnetic field effect of a⁸S_7/2-z⁶P_7/2 lines of ¹⁵¹Eu and ¹⁵³Eu in magnetic fields up to 66.7 mT has been studied by using laser atomic beam spectroscopy. The Zeeman level structures of the europium a⁸S_7/2 and z⁶P_7/2 states in magnetic fields were discussed. The location and intensity of the measured Zeeman transition lines were found in good agreement with the theoretical results.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

Domain-like magnetic structure in superconductors of ErRh4B4 and HoMo6S8 type

The problem of the coexistence of superconductivity and magnetic order is studied by taking into account the indirect exchange interaction, magnetic dipolar interaction and magnetic anisotropy. It is shown that the domain-like magnetic structure should be realized in the superconducting phases of ErRh₄B₄ and HoMo₆S₈ at the temperatures T_m = 1.4 and 0.7 K respectively. The transition from superconducting domain-like phase (DS) to the normal ferromagnetic (FN) state is described.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

Magnetic structure of V5S8

The magnetic structure of V₅S₈ has been investigated by neutron diffraction at low temperature. Two single crystals (sample 1 and sample 2) grown by the same procedure gave considerably different results. Sample 1 was found to have an incommensurate structure, while sample 2 was found to have simple collinear antiferromagnetic structure consistent with magnetic measurements. Although the positions of the magnetic diffraction peaks of sample 1 were close to those of sample 2, the neutron intensity behavior was quite different and the detailed structure could not be determined in the case of sample 1. In both samples, the magnitude of the moments was evaluated to be much larger than the value estimated from NMR.     

Salting-out in intercalation compounds: Removing copper from Cu3Mo6S8 by intercalating lithium

We study the removal of the copper in Cu₃Mo₆S₈ by the intercalation of lithium. For 0<×<1, Li_xCu₃Mo₆S₈ is a single phase compound. For x?1, the copper atoms are forced out of the Mo₆S₈ host. We present a lattice-gas model which shows how the intercalation of Li can force the Cu out of the host.     

GEOMETRIC AND ELECTRONIC STRUCTURES OF Ti8C12 CLUSTER

The electronic structure of Ti₈C₁₂ clusters with three possible geometric structures suggested in the literature is studied using the discrete-variational local-density-functional method. The results show that the ground states of the clusters are all degenerate, which means further Jahn-Teller distortions for the geometric structures of clusters. The results also indicate that the distorted dodecahedral Ti₈C₁₂ cluster, which is proposed by Guo et al. and optimized by the first principle calculations, is the most stable one among the clusters we considered and its electronic structure can explain the experimental observations. In this cluster, there is a strong pd bonding between Ti and C atoms, and the density of states at the Fermi energy is high.