High-pressure syntheses of TaS3, NbS3, TaSe3, and NbSe3 with NbSe3-type crystal structure

Transition metal trichalcogenides TaSe₃, TaS₃, NbSe₃ and NbS₃ were prepared under the reaction conditions of 2 GPa, 700°C, 30 min. NbSe₃ is exactly the same as that obtained in the usual sealed-tube method. The other products are modifications of each usual phase. They have crystal structures very similar to that of NbSe₃. The lattice parameters are a = 10.02Å, b = 3.48 Å, c = 15.56 Å, β = 109.6° for TaSe₃, a = 9.52 Å, b = 3.35 Å, c = 14.92 Å, β = 110.0° for TaS₃, and a = 9.68 Å, b = 3.37 Å, c = 14.83 Å, β = 109.9° for NbS₃. In spite of the similarity in their crystal structures, these high-pressure phases show a variety of electrical transport properties. TaSe₃ is a superconductor having T_c at 1.9 K. TaS₃ is a semiconductor with two transitions at 200 and 250 K. NbS₃ is a semiconductor with E_a = 180 MeV.     

Intercalation phases of TiS2, 2HNbS2, and 1TTaS2 with ethylenediamine and trimethylenediamine: A crystal chemical and thermogravimetric study

The title compounds were prepared and chemicaly analyzed. Their crystal structures were determined from rotating crystal photographs. 1T-, 2H-, and two different 3R-polymorphs were observed. The thermogravimetric analysis, revealing two to four distinct steps for the phases derived from TiS₂ and 2HNbS₂, and only one to two smeared-out steps for those derived from 1TTaS₂, proves the coexistence of strongly and weakly bound intercalate molecules. The first ones cannot be thermally deintercalated without chemical decomposition. The results are discussed within the framework of an ionic bonding model.     

XPS study of one-dimensional compounds: TiS3

X-Ray photoelectron spectra of TiS₃ with a one-dimensional structure were measured. TiS₃ may be regarded as Ti⁴⁺(S₂)^2?S^2? with pairs of S atoms (S₂) and isolated S atoms. The spectra of the sulfur core-levels are assigned by comparison with those of TiS₂, where all S atoms are largely separated. The binding energy of the S₂ pairs is found to be 1.4 eV higher than that of the isolated S atoms, which is consistent with the larger negative charge of the isolated atoms. The structures of the valence band of TiS₃ are discussed in terms of a molecular orbital scheme for the S₂ pairs.     

Crystal, electronic structures and photoluminescence properties of rare-earth doped LiSi2N3

The crystal and electronic structures, and luminescence properties of Eu²⁺, Ce³⁺ and Tb³⁺ activated LiSi₂N₃ are reported. LiSi₂N₃ is an insulator with an indirect band gap of about 5.0 eV (experimental value ∼6.4 eV) and the Li 2s, 2p states are positioned on the top of the valence band close to the Fermi level and the bottom of the conduction band. The solubility of Eu²⁺ is significantly higher than Ce³⁺ and Tb³⁺ in LiSi₂N₃ which may be strongly related to the valence difference between Li⁺ and rare-earth ions. LiSi₂N₃:Eu²⁺ shows yellow emission at about 580 nm due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. Double substitution is found to be the effective ways to improve the luminescence efficiency of LiSi₂N₃:Eu²⁺, especially for the partial replacement of (LiSi)⁵⁺ with (CaAl)⁵⁺, which gives red emission at 620 nm, showing highly promising applications in white LEDs. LiSi₂N₃:Ce³⁺ emits blue light at about 450 nm arising from the 5d¹→4f¹5d⁰ transition of Ce³⁺ upon excitation at 320 nm. LiSi₂N₃:Tb³⁺ gives strong green line emission with a maximum peak at about 542 nm attributed to the ⁵D₄→⁷F_J (J=3-6) transition of Tb³⁺, which is caused by highly efficient energy transfer from the LiSi₂N₃ host to the Tb³⁺ ions.     

Synthesis, band structure, and optical properties of Ba2ZnV2O8

A novel compound Ba₂ZnV₂O₈ has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P2₁/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV₂O₈⁴⁻]_∞, and the Ba²⁺ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba₂ZnV₂O₈ is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of n_x, n_y, and n_z is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba₂ZnV₂O₈ crystal.     

Incoherent neutron spectra of HxTaS2, a nonstoichiometric covalent tantalum hydrosulfide

Inelastic neutron spectra show the presence of a fundamental hydrogen vibration at 712 and 744 cm^?1 in H_0.1TaS₂ and H_0.5TaS₂, respectively. This permits the structural deduction that H_xTaS₂ is a non-stoichiometric covalent metal hydrosulfide. In H_0.5TaS₂ another low-intensity band in the spectrum may be interpreted as suggesting the presence of a small concentration of SH^? anions. An X-ray diffraction pattern taken after the neutron experiments reveals partial decomposition to TaS₂ and the presence of satellites to the (00l) reflections show the decomposition to be a process involving considerable long-range order.     

Substitution of Co in YBa2Fe3O8

The accommodation of Co in the oxygen-saturated solid-solution phase YBa₂(Fe_1−zCo_z)₃O_8+w has been investigated by powder X-ray and neutron diffraction techniques, as well as by Mössbauer spectroscopy. Of the nominal composition range 0.00?z?1.00 tested, the solid-solution limit under syntheses at 950°C in is z=0.47(5). No symmetry change in the nuclear and magnetic structures is seen as a consequence of the Co substitution, and the Co atoms are distributed evenly over the two sites that are square-pyramidally and octahedrally coordinated for w=0. The oxygen-saturated samples maintain their oxygen content roughly constant throughout the homogeneity range, showing that Co³⁺ replaces Fe³⁺. Despite the nearly constant value of w, Mössbauer spectroscopy shows that the amount of tetravalent Fe slightly increases with increasing z, and this allows Co to adopt valence close to 3.00 to a good approximation. The magnitude of the antiferromagnetic moment (located in the a,b plane) decreases with z in accordance with the high-spin states of the majority Fe³⁺ and Co³⁺ ions. Bond-valence analyses are performed to illustrate how the structural network becomes increasingly frustrated as a result of the substitution of Fe³⁺ by the smaller Co³⁺ ion. A contrast is pointed out with the substitution of cobalt in YBa₂Cu₃O₇ where it is a larger Co²⁺ ion that replaces smaller Cu²⁺.     

Optical transitions,XPS, electronic states in NiPS3

We have measured the optical absorption below the fundamental threshold, the normal-incidence reflectivity between 1.5 and 30 eV and the X-ray photoemission spectra of NiPS₃. Shake-up satellites present at the Ni 2p and 3p core levels are strong evidence for the ionicity of the NiS bonds. We have also derived a qualitative molecular orbital model of NiPS₃ in which the trigonal crystal field splits the P and S 3p_xp_y-3p_a states, and strong covalent hybridization between P and S p_xp_y orbitals leads to covalent electronic bonding. Ni is envisaged as a divalent ion which plays little role in the electronic bonding and its 3d levels are localized, lying near the top both of the valence states. This model accounts well for both the valence band XPS data and the low energy optical transitions. Our model should represent, at the center of the Brillouin zone but not at the boundaries, the energy level sequence in NiPS₃ and other related MPX₃ layer-type compounds where M Co²⁺, Mn²⁺, Fe²⁺, Zn²⁺ and X is sulfur or selenium.The XPS spectra and optical properties of NiPS₃ have been obtained and interpreted on a qualitative molecular orbital model in which the Ni is a divalent positive ion which plays little role in the bonding. Evidence for such ionicity appears in the optical properties and XPS satellite structures, as well as in the magnetic properties. The model should represent qualitatively the band structure at the center of the Brillouin zone, but not at the boundaries. It should also be valid for other compounds similar to NiPS₃, i.e. those with other metals in place of Ni and those with Se in place of S.     

Crystal Structures and Magnetic Properties of the Two Misfit Layer Compounds: [SrGd0.5S1.5]1.16 NbS2 and [Sr(Fe,Nb)0.5S1.5]1.13 NbS2

Crystal structures of two new misfit compounds, [SrGd_0.5S_1.5]_1.16NbS₂ and [Sr(Fe,Nb)_0.5S_1.5]_1.13NbS₂, were determined through the composite approach, i.e., by refining each subpart (Q, H-parts, and the common part) of these composite materials, separately. The Q-part is a three-atom-thick layer, with the NaCl-type structure, where external SrS planes enclose the inner GdS or (Fe,Nb)S plane; the structural difference between these two compounds lies in the central layer within the Q-part: Gd and S atoms are in special positions (octahedral coordination), while Fe and S atoms are statistically distributed on split (×4) positions (tetrahedral coordination) around a central unique site (=special position occupied by Nb). The H-part is a sandwich of sulfur planes enclosing the inner Nb plane as observed for the structure of the binary compound NbS₂ itself. The Sr-Gd derivative shows a paramagnetic behavior in the whole studied temperature range (2-300 K). On the other hand, antiferromagnetic interactions occur in the Sr-Fe derivative; the complex magnetic behavior of this compound is related to the statistical distribution of Fe atoms which leads to frustration of the magnetic interactions. At room temperature, experimental values obtained from Mössbauer spectrum correspond to Fe³⁺ in tetrahedral sulfur environment: isomer shift δ=0.32 mm s⁻¹, and quadrupole splitting ΔE=0.48 mm s⁻¹.     

Visible‐Light‐Induced Generation of H2 by Nanocomposites of Few‐Layer TiS2 and TaS2 with CdS Nanoparticles

Graphene analogues of TaS₂ and TiS₂ (3–4 layers), prepared by Li intercalation followed by exfoliation in water, were characterized. Nanocomposites of CdS with few‐layer TiS₂ and TaS₂ were employed for the visible‐light‐induced H₂ evolution reaction (HER). Benzyl alcohol was used as the sacrificial electron donor, which was oxidized to benzaldehyde during the reaction. Few‐layer TiS₂ is a semiconductor with a band gap of 0.7 eV, and its nanocomposite with CdS showed an activity of 1000 μmol h^?1 g^?1_. The nanocomposite of few‐layer TaS₂, in contrast, gave rise to higher activity of 2320 μmol h^?1 g^?1, which was attributed to the metallic nature of few‐layer TaS₂. The amount of hydrogen evolved after 20 and 16 h for the CdS/TiS₂ and CdS/TaS₂ nanocomposites was 14833 and 28132 μmol, respectively, with turnover frequencies of 0.24 and 0.57 h^?1, respectively.     

Electronic structures and X-ray photoelectron spectra of MoO2 and Li2 MoO4

Electronic structures of MoO₂ (4d²) and molybdatc (4d^o) are calculated by the discrete-variational Xα method employing [Mo₂O₁₀^12? and [MoO₄]^2? clusters. The calculations indicate that the Mo—O bond is more covalent in the molybdatc than in MoO₂. Level structures for the valence band region arc in agreement with XPS spectra of MoO₂ and Li₂MoO₄.     

Synthesis, structural characterization and Li ion conductivity of a new vanado-molybdate phase, LiMg3VMo2O12

A new vanado-molybdate LiMg₃VMo₂O₁₂ has been synthesized, the crystal structure determined an ionic conductivity measured. The solid solution Li_2−zMg_2+zV_zMo_3−zO₁₂ was investigated and the structures of the z=0.5 and 1.0 compositions were refined by Rietveld analysis of powder X-ray (XRD) and powder neutron diffraction (ND) data. The structures were refined in the orthorhombic space group Pnma with a∼5.10, b∼10.4 and c∼17.6 Å, and are isostructural with the previously reported double molybdates Li₂M₂(MoO₄)₃ (M=M²⁺, z=0). The structures comprise of two unique (Li/Mg)O₆ octahedra, (Li/Mg)O₆ trigonal prisms and two unique (Mo/V)O₄ tetrahedra. A well-defined 1:3 ratio of Li⁺:Mg²⁺ is observed in octahedral chains for LiMg₃VMo₂O₁₂. Li⁺ preferentially occupies trigonal prisms and Mg²⁺ favours octahedral sheets. Excess V⁵⁺ adjacent to the octahedral sheets may indicate short-range order. Ionic conductivity measured by impedance spectroscopy (IS) and differential scanning calorimetry (DSC) measurements show the presence of a phase transition, at 500-600 °C, depending on x. A decrease in activation energy for Li⁺ ion conductivity occurs at the phase transition and the high temperature structure is a good Li⁺ ion conductor, with σ=1×10⁻³-4×10⁻² S cm⁻¹ and E_a=0.6 to 0.8 eV.     

Analysis of the electronic structure of Hf(Si0.5As0.5)As by X-ray photoelectron and photoemission spectroscopy

The ternary hafnium silicon arsenide, Hf(Si_xAs_1−x)As, has been synthesized with a phase width of 0.5?x?0.7. Single-crystal X-ray diffraction studies on Hf(Si_0.5As_0.5)As showed that it adopts the ZrSiS-type structure (Pearson symbol tP6, space group P4/nmm, Z=2, a=3.6410(5) Å, c=8.155(1) Å). Physical property measurements indicated that it is metallic and Pauli paramagnetic. The electronic structure of Hf(Si_0.5As_0.5)As was investigated by examining plate-shaped crystals with laboratory-based X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoemission spectroscopy (PES). The Si 2p and As 3d XPS binding energies were consistent with assignments of anionic Si¹⁻ and As^1-. However, the Hf charge could not be determined by analysis of the Hf 4f binding energy because of electron delocalization in the 5d band. To examine these charge assignments further, the valence band spectrum obtained by XPS and PES was interpreted with the aid of TB-LMTO band structure calculations. By collecting the PES spectra at different excitation energies to vary the photoionization cross-sections, the contributions from different elements to the valence band spectrum could be isolated. Fitting the XPS valence band spectrum to these elemental components resulted in charges that confirm that the formulation of the product is Hf²⁺[(Si_0.5As_0.5)As]²⁻.     

Partial substitution of rhodium for cobalt in the misfit [Pb0.7Co0.4Sr1.9O3][CoO2]1.8 oxide

The partial substitution of Co by Rh in the [Pb_0⋅7Co_0.4Sr_1.9O₃]^RS[CoO₂]_1.8 family has been investigated. By transmission electron microscopy and X-ray powder diffraction, it is shown that the substitution of Rh for Co takes place at the two cobalt sites of the structure but for the low enough Rh contents, this substitution is made preferentially at the level of the CdI₂-like layer. Thus, a generic formula [Pb_0.7(Co_0.4−zRh_z)Sr_1.9O₃]^RS[Co_1−yRh_yO₂]_b1/b2 (0?y?0.5 and 0?z?0.3) can be proposed for this new family of misfit phase. As observed for the pure misfit cobaltite, the thermoelectric power is also very large, close to +140 μV/K at room temperature. The Rh cation can adopt a mixed valency Rh³⁺/Rh⁴⁺ (4d⁶/4d⁵) with low spin states t_2g⁶/t_2g⁵ equivalent to the ones of low spin Co³⁺/Co⁴⁺ (3d⁶/3d⁵). The large thermopower observed in the Rh substituted compounds is therefore a direct proof that the coexistence of low spin states t_2g⁶/t_2g⁵ contributes to the thermoelectric power enhancement in these oxides.     

FeGa3 and RuGa3: Semiconducting Intermetallic Compounds

The intermetallic compounds FeGa₃ and RuGa₃ were prepared from the elements using a Ga flux and their structures were refined from single-crystal X-ray data. Both compounds crystallize with the FeGa₃ structure type (tetragonal, space group P4₂/mnm, Z=4). Electrical resistivity measurements revealed a semiconducting behavior for FeGa₃ and RuGa₃, which is in contrast to the good metallic conductivity observed for the isotypic compound CoGa₃. The origin of the different electronic properties of these materials was investigated by first-principle calculations. It was found that in compounds adopting the FeGa₃ structure type the transition metal atoms and Ga atoms interact strongly. This opens a d-p hybridization bandgap with a size of about 0.31 eV in the density of states at the Fermi level for 17-electron compounds (i.e., FeGa₃ and RuGa₃). The electronic structure of CoGa₃ (an 18-electron compound) displays rigid band behavior with respect to FeGa₃. As a consequence, the Fermi level in CoGa₃ becomes located above the d-p hybridization gap which explains its metallic conductivity.     

CAS SCF Cl calculations for the 3Σ−g, 1Σ+g, 3Σ+u, and 5Δu states of Sc2

CAS SCF CI (SD) calculations have been carried out for the ³Σ^?_g, ¹Σ⁺_g, ³Σ⁺_u, and ⁵Δ_u states of Sc₂ using large gaussian basis sets. The ³Σ^?_g, ¹Σ⁺_g, and ³Σ⁺_u states arise from the ²D(4s² 3d¹) + ²D(4s² 3d¹) limit of Sc₂ and are found to be only weakly bound (D_c ≈ 0.06 eV and R_c ≈ 8.0a₀). The ⁵Δ_u state arises from the ²D(4s² 3d¹) + ⁴F(4s¹ 3d¹ 4p¹) atomic limit. This state is found to be strongly bound relative to its limits (D_c ≈ 0.8 eV and R_c ≈ 7.0a₀).     

Electronic structure and properties of NbS3 and Nb3S4

Electronic structure calculations for NbS₃ and Nb₃S₄ are reported. The NbS₃ structure is closely related to that of ZrSe₃. In the undistorted ZrSe₃ atomic arrangement, NbS₃ would be a metal; it is shown that the observed distortion, a pairing of Nb atoms along the b-axis relative to ZrSe₃, stabilizes the NbS₃ crystal by inducing a 0.5-eV semiconducting gap. Nb₃S₄ is found to be a metal with the Fermi level lying near a deep minimum in the density of electron states.     

The luminescence of Cs3Bi2Cl9 and Cs3Sb2Cl9

The luminescence properties of Cs₃Bi₂Cl₉, α-Cs₃Sb₂Cl₉, and β-Cs₃Sb₂Cl₉ are reported and compared with those of Cs₃Bi₂Br₉. The first two compounds have comparable luminescence properties which can be described in terms of a band model. Deep center emission is observed for both compounds, whereas edge emission is observed only for Cs₃Bi₂Cl₉. The optical transitions of β-Cs₃Sb₂Cl₉ are localized on the Sb³⁺ ion. The orientation of the lone-pair orbitals of the ns² ions seems to play an important role in the formation of the cationic valence band. The α-β transformation must therefore have a considerable influence on the spectral properties of Cs₃Sb₂Cl₉.     

The relevancy of the [B2N4] substructure in the electronic structure of the metal-rich lanthanum nitridoborate La3(B2N4)

Lanthanoide nitridoborates of the general formula Ln₃(B₂N₄) with Ln=La, Ce, Pr, and Nd occur as black crystalline materials. Their structures contain oxalate-like [B₂N₄]⁸⁻ ions being stacked in an eclipsed formation along one crystallographic direction. Electronic structures were calculated for a molecular [B₂N₄]⁸⁻, for the [B₂N₄] partial structure, and for the complete La₃(B₂N₄) structure with the extended Hückel algorithm to analyze the bonding characteristics and to trace the necessity and properties of one surplus electron of (La³⁺)₃(B₂N₄⁸⁻)(e⁻). The HOMO of a [B₂N₄]⁸⁻ is B-B σ bonding, and the LUMO is B-B π bonding but B-N antibonding. The energy band of the solid state [B₂N₄] partial structure corresponding to the LUMO is broadened as a result of intermolecular B?B interactions between adjacent [B₂N₄] units along the stacking direction. Due to bonding interactions with La d orbitals, this band is significantly lowered in energy and occupied with one electron in the band structure of La₃(B₂N₄). This singly occupied band exhibits no band crossings but creates a semimetal-like band structure situation.     

Structure and properties of ordered Li2IrO3 and Li2PtO3

The structures of Li₂MO₃ (M=Ir, Pt) can be derived from the well-known Li-ion battery cathode material, LiCoO₂, through ordering of Li⁺ and M⁴⁺ ions in the layers that are exclusively occupied by cobalt in LiCoO₂. The additional cation ordering lowers the symmetry from rhombohedral (R-3m) to monoclinic (C2/m). Unlike Li₂RuO₃ no evidence is found for a further distortion of the structure driven by formation of metal-metal bonds. Thermal analysis studies coupled with both ex-situ and in-situ X-ray diffraction measurements show that these compounds are stable up to temperatures approaching 1375 K in O₂, N₂, and air, but decompose at much lower temperatures in forming gas (5% H₂:95% N₂) due to reduction of the transition metal to its elemental form. Li₂IrO₃ undergoes a slightly more complicated decomposition in reducing atmospheres, which appears to involve loss of oxygen prior to collapse of the layered Li₂IrO₃ structure. Electrical measurements, UV-visible reflectance spectroscopy and electronic band structure calculations show that Li₂IrO₃ is metallic, while Li₂PtO₃ is a semiconductor, with a band gap of 2.3 eV.