Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [Fe 2 III FeIIO(C2H5CO2)6(py)3]npy;n=0, 1.5

Mixed-valence trinuclear iron propionates [Fe ₂ ^III Fe^IIO(C₂H₅CO₂)₆(py)₃]npy, wheren=0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Mössbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature.     

Mössbauer and molecular orbital (MO) study of localized and delocalized mixed-valence organo-FeIIFeI bisandwiches

A Mössbauer study of two mixed-valence Fe^IIFe^I compounds C₅H₅Fe(C₅H₄)₂ FeC₆(CH₃)₆ (1) and ¦C₆(CH₃)₆ Fe(C₅H₄)₂ Fe C₆(CH₃)₆¦⁺ (2 ⁺) was carried out from 4.2K to room temperature. Zero-field spectra show two types of iron atoms for1 and one type for2 ⁺. Hence1 is a localized mixed-valence complex and2 ⁺ a delocalized mixed-valence complexe. High magnetic field spectra for 2⁺ give a negative sign for the EFG and show the valence electron is delocalized on the two centers. IEHT-MO calculations confirm the results and allow to explain the temperature independence of the quadrupole splitting (QS) of2 ⁺.     

Synthesis and optical properties for crystals of a novel organic semiconductor [ Ni(Cl) 2{(Ph 2P) 2CHC(R 1R 2)NHNH 2}]

In this investigation, the synthesis process of the apyrazole derivative for diphenylphosphino-methane hydrazine complexes [ Ni(Cl)₂{(Ph₂P)₂CHC(R₁R₂)NHNH₂}] was reported, and the obtained crystals were analyzed by X-ray diffraction. As a result of the growth process, a set of complexes were formed. The structures of these complexes are discussed on the basis of Elemental analysis (EA), IR, ¹H-NMR, ³¹P-NMR spectroscopic data and FAB mass spectra. The compound under investigation shows typical semiconductor behavior as a result of delocalization of the π-electrons in the structure. The reflectance and transmittance spectra for the crystals were measured and analyzed in the incident photon energy range 1.29 to 3.93 eV and in the temperature range 77 to 300 K. The optical study revealed that the optical transition is direct allowed. Below the absorption edge, the refractive index as a function of wavelength was determined in the low energy region of the used incident photon energy range. From the refractive index-wavelength variations, the oscillator and dispersion energies of the refractive index for the obtained crystals were determined. The static refractive index and static dielectric constant were evaluated.     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Thermochromic Phase Transition in [NH2(C2H5)2]2CuCl4 Crystals

The absorption spectra of [NH₂(C₂H₅)₂]₂CuCl₄ crystals in the visible spectral region in the vicinity of the thermochromic phase transition at T ₁ = 311 K are investigated. It is shown that in these crystalline compounds the phenomenon of thermochromism is primarily associated with the change of the plane-quadratic geometry of the coordination environment of Cu²⁺ to the tetrahedral form. The influence of ionizing irradiation on the phase-transition temperature and on the thermochromic properties of this crystal is studied.     

The Growth of P-type TlGaSe2(1−x) S2x Single Crystals

TlGaSe_2(1–x) S_2x single crystals were grown by the modified Bridgman-Stockbarger method in our crystal growth laboratory. A^IIIB^III C₂ ^VI compounds are formed of elements from vertical groups of the periodic table (group III: Tl, Ga, In; group VI: Se, S, Te) and are classified into two types. The first type has a layer structure: TlGaSe₂, TlGaS₂ and TlInS₂. The second type has a chained structure: TlInSe₂, TlInTe₂ and TlGaTe₂. None of the grown crystals had cracks and voids on the surface. The freshly cleaved crystals had a mirror-like surface and there was no need for mechanical or chemical polishing treatments. By the hot probe technique, we have found that the crystals were of p-type. The ingots produced were single crystalline and the useful region of single crystal was 90% with steps of 10 K if changes were small, and with steps of 3 and 5 K if changes were large in the direct and indirect band gaps energies. The direct and indirect band gaps for TlGaSe_2(1–x)S_2x samples were calculated as a function of temperature.     

Thermo-and photostimulated luminescence of CaI2: Tl and CaI2: Pb crystals

Thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb scintillation crystals under optical and X-ray excitation is studied. It is shown on the basis of the results obtained with account for the data of studies of photo-and X-ray-luminescent properties of these scintillators that Tl⁺ and Pb²⁺ ions form complex capture centers with host defects. These centers are responsible for the thermostimulated luminescence in the temperature range of 150–295 K, and the centers of charge carrier trapping are spatially separated from the centers of recombination emission. An assumption is made that thermo-and photostimulated luminescence of CaI₂: Tl and CaI₂: Pb crystals under optical excitation is observed mainly due to the delocalization of charge carriers from hydrogen-containing centers responsible for the excitation band at 236 nm and the photoluminescence of CaI₂ with a maximum at 395 nm. The luminescence of CaI₂: Tl crystals in the 510-nm band and CaI₂: Pb crystals in the 530-nm band is determined by the radiative decay of near-activator excitons.     

EPR and optical-absorption studies of Cu2+-doped Zn(NH2(CH2)3NHOH)2Ni(CN)4 single crystals

Electron paramagnetic resonance of Cu²⁺-doped catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-μ-cyanonicelate(II) [Zn(NH₂(CH₂)₃NHOH)₂Ni(CN)₄] single crystals and powder are examined at room temperature. The spectra show the substitution of the Zn²⁺ ion with the Cu²⁺ ion. The crystal field around the Cu²⁺ ion is nearly axial. There is a single paramagnetic site withg _xx=2.073,g _yy=2.060,g _zz=2.248,A _xx=40.5 G,A _yy=50.8 G,A _zz=172.0 G. The ground-state wave function is an admixture of d _x ²−y ² and d _z ² states. The optical-absorption studies show two bands at 320 nm (31250 cm⁻¹) and 614 nm (16286 cm⁻¹) which confirm the axial symmetry. The crystal field parameters and the wave function are determined.     

Variable temperature Mössbauer spectroscopic studies of oxo-centered trinuclear mixed-valence iron succinate, mesaconate and isophthalate complexes

Three new oxo-centered trinuclear mixed-valence iron complexes, iron succinate, iron mesaconate and iron isophthalate have been prepared. Temperature dependent valence delocalization processes were observed for all the complexes on variable temperature Mössbauer spectroscopic studies. Two clear quadrupole split doublets attributed to high-spin Fe(III) and high-spin Fe(II) states were existed for the complexes at liquid nitrogen temperature. At room temperature a nearly averaged singlet peak was observed for mesaconate complex and averaged doublet peaks were observed for succinate and isophthalate complexes with IS values 0.68 and 0.68 mms^?1 and QS values 0.44 and 0.48 mms^?1 respectively.     

X-ray Photoelectron Spectroscopy of Sb2S3 Crystals

The paper presents the X-ray photoelectron spectra (XPS) of the valence band and core levels of semiconductor ferroelectric Sb₂S₃ single crystals, which show weak phase transitions and anomalies of various physical properties. The XPS were measured with monochromatized Al K _α radiation in the energy range 0-1450 eV and the temperature range 160-450 K. The valence band is located 0.8-7.5 eV below the Fermi level. Experimental results of the valence band and core levels are compared with the results of theoretical ab initio calculations of the molecular model of Sb₂S₃ crystal. The chemical shifts in Sb₂S₃ crystal for the Sb and S states are obtained. Results revealed that the small structural rearrangements at the phase transition T _c1 = 300 K shift the Fermi level and all electronic spectrum. Also, temperature dependence of a spontaneous polarisation shifts the electronic spectra of the valence band and core levels. Specific temperature-dependent excitations in Sb 3d core levels are also revealed.     

Temperature evolution of the intra-ion absorption spectra of (NH2(C2H5)2)2CoCl4 crystals in the region of their phase transitions

On the basis of spectroscopic studies of (NH₂(C₂H₅)₂)₂CoCl₄ crystals, the absorption bands corresponding to the internal electronic transitions in the Co²⁺ ion were identified. The values of the crystal field and Racah parameters were calculated. The temperature evolution of the absorption spectra of (NH₂(C₂H₅)₂)₂CoCl₄ crystals reveals the anomalies of their parameters at the points of phase transitions. The corresponding changes of the absorption spectra were discussed in terms of distortion of the metal-halogen complex. The temperature dependences of the absorption spectra of (NH₂(C₂H₅)₂)₂CoCl₄ crystals confirm the presence of the thermochromic phase transitions at 255 and 330?K.     

NpAs2: Magnetic form factor and tentative crystal field model

A polarized neutron diffraction experiment at 4.2 K was carried out on two NpAs₂ single crystals with different orientations of the crystallographic axes with respect to the magnetic field. Low temperature atomic positions are given together with the Fermi length of the Np atom: 1.015X10^-12cm. The valence state of the Np ion is 4+, the ordered moment value is 1.46μ_B, a strong magnetocrystalline anisotropy and a field variation of the ordering temperature have been evidenced for the ferromagnetic state. 58 magnetic structure factors have been measured. A tentative crystal field model is presented.     

Optical studies of (NH4)2SO4 single crystal in the paraelectric phase

Transmittance and absorbance spectra of (NH₄)₂SO₄ single crystals along [010] direction were measured at different temperatures (296, 308, 318, 328 and 348 K) in the paraelectric phase. The absorption coefficient was computed and the analysis of the data revealed the existence of two optical transitions in (NH₄)₂SO₄ single crystals. The direct and indirect band gaps were shifted towards the longer wavelength with increasing temperature. The data on the allowed indirect transition was analyzed and interpreted in terms of two valence bands originated by spin orbit interaction and crystal field splitting. The momenta E_p were calculated as the difference between E_g1, the first valence to conduction band, and E_g2 for the second valence band at different temperatures. The results of extinction coefficient (k), the refractive index (n), and dielectric constants (ε) were also discussed and calculated as a function of wave length (λ). The heat treatment of the crystals proved that the variations of these optical parameters can be consequence of the internal microstructure changes caused by annealing.     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.     

AgGaSe2 : A highly photoconductive material

High resistivity single crystals of AgGaSe₂ were grown by the horizontal Bridgman technique. The near band edge photoconductivity of the grown crystal at room temperature was found to be up to 2×10⁴ times higher than the dark conductivity, under the illumination of 10⁻³ W/cm². The photoconductivity spectrum consists primarily of three peaks, which are attributed to the transitions from Γ₇(A), Γ₆(B) and Γ₇(C) states of valence band to the conduction band Γ₆. The crystal field splitting and the spin-orbit splitting were determined from these peak energy positions of the photoconductivity spectrum.     

Thermal decay of photochromic color centers in CaF2, SrF2, and BaF2 crystals doped by La and Y impurities

The absorption spectra of photochromic centers in CaF₂, SrF₂, and BaF₂ crystals doped by La and Y impurities and thermal decay of the centers in the temperature range 80–600 K are investigated. Under low-temperature x-ray irradiation, ionized photochromic color (PC⁺) centers are generated in La- and Y-doped CaF₂ crystals and in a La-doped SrF₂ crystal. It is revealed that, upon heating of the CaF₂-LaF₃ crystal, PC⁺ centers are transformed into photochromic color (PC) centers. In the SrF₂-YF₃ crystal irradiated at room temperature, photochromic color centers are generated as well. All color centers decay at a temperature of approximately 600 K. After irradiation of the BaF₂-YF₃ crystal at a temperature of 80 K, absorption bands are observed at energies of 2.25 and 3.60 eV, which are related to neither PC centers nor PC⁺ centers.     

The electronic structure of ilvaite and the pressure and temperature dependence of its 57Fe Mössbauer spectrum

⁵⁷Fe Mössbauer measurements have been performed on four, chemically analyzed samples of the mixed-valence mineral ilvaite, Fe³⁺Fe₂²⁺(Si₂O₇)O(OH), as polycrystals and oriented-single-crystals between 300 and 475 K and between 1 and 60,000 bar. At 1 bar and T < 400 K, four absorption features are necessary to account for the spectral envelopes: Three are quadrupole doublets which are assigned to the three crystal/chemical species of iron but not without some ambiguities regarding the appropriate electronic structure. Only the doublet assigned to Fe²⁺ on 4c (space group Pnma) corresponds to that of an orthodox, high-spin Fe²⁺ ion. The remaining two doublets are assigned to nominal Fe²⁺ and Fe³⁺ on the 8d site but have hyperfine parameters that exhibit anomalous values and temperature dependences, which lead to a coalescence at ～400K into a single “Fe³⁺-like” doublet. These phenomena are interpreted as arising from a delocalization primarily of the d-electron from the 8d Fe²⁺ ion into a band-like, itinerant state. For (001) oriented crystals, the influence of pressure is remarkable and features associated with extensive electron delocalization in the high temperature spectra are highly developed even at 30kb and 298 K, indicating enhanced electron delocalization as a result of decreased internuclear separations parallel to the infinite ribbons of 8d sites. The spectra of polycrystalline and oriented-(100) and -(010) absorbers change more slowly with pressure and 60 kb pressure is required to achieve the effects of 30 kb on a (001) absorber. The fourth feature in the spectrum consists of a broad absorption at ～1.5mms^?1 and is tentatively assigned to an electronic state of minor importance due to electron transfer between localized Fe²⁺ and Fe³⁺ centers. The low intensity of this absorption feature, ～10% of the total, probably accounts for its neglect by other investigators.     

Double exchange in cubic crystals with pairs of exchange-coupled mixed-valence 3<Emphasis Type="Italic">d</Emphasis><Superscript>3</Superscript>-3<Emphasis Type="Italic">d</Emphasis><Superscript>4</Superscript> ions

Specifics of the exchange interaction in mixed-valence Cr²⁺–Cr³⁺ 3d-ion pairs in KZnF₃ crystals are studied. It is shown that the double-exchange interaction can be significantly reduced by the low-symmetry crystal field created by a compensator. The features of the exchange interaction and optical absorption spectra are qualitatively analyzed.     

Electronic structure of rutile SnO2, GeO2 and TeO2

The electronic structure of SnO₂, GeO₂ and TeO₂ in the rutile crystal structure is calculated using the scalar-relativistic linear muffin-tin-orbital method. Good accordance between the calculated energy bands and experimental information is found. Some important qualitative discrepancies remain, demonstrating the delicacy of the problem of obtaining the electron energies of relatively low symmetry ionic crystals from first principles. The crystal charge distribution reveals a significant admixture of covalency in the bonding of the rutile dioxides, and the appropriate charge state of the cation turns out to be far from the ideal ionic + 4 configuration. This has an important impact on the interpretation of Mössbauer experiments with the ¹¹⁹Sn and ⁷³Ge isotopes as the valence contribution to the electron density on the nuclear site is substantial.     

EPR and Optical Absorption Studies of VO2+-Doped Diammonium Hexaaqua Magnesium(II) Sulfate

Electron paramagnetic resonance (EPR) studies of VO²⁺ impurity ion in single crystals of diammonium hexaaqua magnesium(II) sulfate are carried out at 9.5 GHz (X-band) at room temperature. Different spin-Hamiltonian parameters are determined. VO²⁺ is expected to enter the lattice substitutionally. Superhyperfine splitting is also observed. An EPR study of a powder sample is done that supports the data obtained from single crystal studies. Optical absorption studies are also performed at room temperature. The crystal field parameter (D_q), tetragonal parameters (D_s and D_t), and various bonding parameters are evaluated to estimate the covalency and nature of bonding of VO²⁺ with its different ligands.