Energy and optical absorption spectra of endohedral metallofullerenes with Gd or Ho as strongly correlated π-electron systems

Isomerically pure endohedral metallofullerenes Gd@C82(C2v), Ho@C₈₂(C_2v), and their monoanions have been synthesized and separated. The optical absorption spectra of solutions of obtained compounds in o-dichlorobenzene have been studied. Within the Hubbard model, the energy spectrum of isomer of C_2v symmetry (no. 9) of fullerene С₈₂ has been calculated. Based on the obtained spectrum, optical absorption spectra of endohedral metallofullerenes Gd@C₈₂ and Ho@C₈₂ and their monoanions have been simulated. The calculated optical absorption spectra have been compared with experimental ones; it has been found that qualitative agreement between them is observed.     

Na5, Na6和Na7团簇光学吸收谱的理论研究

以含时密度泛函理论为基础，结合从头赝势方法运用含时局域密度近似计算了Na₅，Na₆和Na₇团簇的动力学极化强度，并通过傅里叶变换得出了团簇的光学吸收谱.研究表明，计算结果可以较好地再现实验谱，而且Na₆和Na₇团簇的结果和组态相互作用的结果符合较好.二维结构和三维结构的Na₆团簇的计算结果表明，只有二维结构可出现低于2 eV以下的峰，而且二维结构光谱的计算结果与实验结果符合较好. 关键词： 光吸收谱 Na团簇 含时局域密度近似     

Optical and acoustic properties of TeO2/WO3 glasses with small amount of additive ZrO2

The optical and acoustic properties of tellurite glasses in the system TeO₂/ZrO₂/WO₃ have been investigated. The refractive index at different wavelengths and the optical spectra of the glasses have been measured. From the refractive index and absorption edge studies for prepared glasses, the optical parameter viz; optical band gap (E_opt), Urbach energy, (ΔE), dispersion energy, E_d, and the average oscillator energy, E₀, have been calculated. Sound velocities were measured by pulse echo technique. From these velocities and densities values, various elastic moduli were calculated. The variations in the refractive index, optical energy gap and elastic moduli with WO₃ content have been discussed in terms of the glass structure. Quantitatively, we used the bond compression model for analyzing the room temperature elastic moduli data. By calculating the number of bonds per unit volume, the average stretching force constant, and the average ring size we can extract valuable information about the structure of the present glasses.     

Spectroscopic study of nanocrystalline V2O5·nH2O films doped with Li ions

Optical properties of nanocrystalline, Li_xV₂O₅·nH₂O films (0<x<22 mol%), are explored in the present work. These films have been produced by the sol–gel technique (colloidal route), which was used for the preparation of high purity and homogeneity films. Optical measurements were carried out using a double-beam spectrophotometer. The optical constants such as refractive index n, the extinction coefficient k, absorption coefficient α, and optical band gap of the films material have been evaluated. The optical absorption coefficient was calculated from the measured normal reflectance, R, and transmittance, T, spectra. The optical spectra of all samples exhibited two distinct regions: at high energy, which suggests a direct forbidden transition with optical gap ranging from 1.75 to 2.0 eV and increases with increase in Li-content. On the other hand a second low-energy band suggests a direct allowed transition with optical gap ranging from 0.40 to 0.42 eV. The width of the localized states (band tail) E_e was also estimated for all samples. Additional calculations applying the real part of the optical dielectric function led to the evaluation of the charge carrier concentration and their effective mass.     

Specific features of the electronic structure and spectral properties of NdNi5 − x Cu x compounds

The spectral properties of the intermetallic compounds NdNi_{5 ? x} Cu _x (x = 0, 1, 2) have been studied using optical ellipsometry in the wavelength range 0.22–16 μm. It has been established that substitution of copper atoms for nickel leads to noticeable changes in the optical absorption spectra, plasma frequencies, and relaxation frequencies of conduction electrons. Spin-polarized calculations of the electronic structure of these compounds have been performed in the local spin density approximation allowing for strong electron correlations (LSDA + U method) in the 4f shell of the rare-earth ion. The calculated electron densities of states have been used to interpret the experimental dispersion curves of optical conductivity in the interband light absorption region.     

Optical polarized properties related to the oxygen vacancy in the CaMoO4 crystal

The electronic structures, dielectric functions and absorption spectra for the CaMoO₄ (CMO) crystal with and without oxygen vacancy V_O²⁺ have been calculated using the CASTEP code with the lattice structure optimized. The calculated results indicate that the optical properties of the CMO crystal show anisotropy and its optical symmetry coincides with the lattice structure geometry of the CMO crystal. The calculated absorption spectra indicate that the perfect CMO crystal does not display absorption band in the visible and near-ultraviolet range. However, in this range, the absorption spectra of the CMO crystal containing V_O²⁺ exhibit one peak at about 1.84 eV (673 nm). It predicates that the 680 nm absorption band is related to the existence of V_O²⁺ in the CMO crystal.     

Optical absorption spectra of Ag11 isomers

The optical absorption spectra of the three most stable structural isomers of the Ag₁₁ cluster were calculated using the time-dependent density functional theory within the Casida formalism. The slightly different spectra of the isomers may permit the identification of the ground-state configuration predominantly present in the laboratory beams based on a direct comparison between the calculated photoabsorption response for the Ag₁₁ isomers and the measured spectra of medium-size silver clusters trapped in noble gas Ar and Ne matrices at different temperatures. This assignment is confirmed by the fact that this isomer has the lowest calculated energy.     

Obtaining the Optical and EPR Parameters of Vanadyl-Doped Sodium Dihydrogen Phosphate Dihydrate Powders by Experimental and Theoretical Methods

In this study, the spin-Hamiltonian parameters (g and A), molecular orbital coefficients, and other spectroscopic properties of vanadyl-doped sodium dihydrogen phosphate dihydrate (NaH₂PO₄·2H₂O) powders have been investigated by experimental and theoretical methods, including electron paramagnetic resonance (EPR) and optical absorption spectroscopies. The results show axially symmetric crystalline field around VO²⁺ ion. The optical absorption spectra exhibit three characteristic bands of VO²⁺ ions in tetragonal symmetry. EPR and optical data were used in a complementary way to calculate spin-Hamiltonian parameters and molecular orbital coefficients. The octahedral and the tetragonal field parameters were theoretically calculated on the basis of crystal field theory. These parameters were used to determine various bonding parameters which characterize the nature of bonding in the complex. The theoretical results are supported by experimental results.     

Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

We have performed complex experimental and theoretical investigations of the spectral-luminescent properties and electronic structure of new phthalocyanine analogs, Mg octaphenylporphyrazine and its derivatives with an annulated thiadiazole or selenadiazole ring instead of two phenyl groups. Fluorescence characteristics have been determined at 293 and 77 K: emission, excitation, and fluorescence polarization spectra; fluorescence quantum yield ?? _F , and lifetime ?? _F . Annulation of a five-membered chalcogen-containing heterocycle leads to splitting of the long-wavelength absorption band Q(0-0) and to the bathochromic shift of its longest wavelength component Q _x (0-0), which increase upon passage from S to Se. At the same time, the fluorescence quantum yield ?? _F and lifetime ?? _F decrease, which is related to the intramolecular heavy-atom effect. The geometric structure of the ground state of the Mg porphyrazine molecules has been determined based on the density functional theory (DFT), and excited electronic states have been calculated with modified parametrization of the INDO/S method, INDO/Sm. Semiquantitatively, the calculated level positions of the lowest Q states and spectral shifts of Mg octaphenylporphyrazine and S-derivative agree with experimental data. For the range of the Soret band, calculated transition energies and their intensity distributions substantially depend on the dihedral angle ?? between a phenyl ring and porphyrazine macrocycle. We show that, based on calculations at the angle ?? = 60°, bands in the observed absorption spectra can be assigned with an accuracy of ??2000 cm^?1.     

Unified calculations of the optical and electron paramagnetic resonance spectral data for Ce ion in Y3Ga5O12 crystal

Seven crystal field energy levels (obtained from the optical spectra) and three g factors g_x, g_y and g_z (obtained from electron paramagnetic resonance (EPR) spectra) for Ce³⁺ ion in Y₃Ga₅O₁₂ crystal are calculated together by diagonalizing a complete energy matrix. The Hamiltonian of this energy matrix includes all the interactions for 4f¹ ion Ce³⁺ in rhombic crystal field and under an external magnetic field, and so the optical and EPR data can be studied in a unified way. The calculated crystal field energy levels are in better agreement with the experimental values than the calculated values in the previous paper, and the g factors (which have not been calculated previously) are explained reasonably. The results are discussed.     

Spectral studies on Cu ions in sodium–lead borophosphate glasses

Electron Paramagnetic Resonance (EPR) and optical absorption spectra of Cu²⁺ ions in sodium–lead borophosphate glasses doped with different concentrations of Cu²⁺ ions have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium–lead borophosphate glasses are present in octahedral sites with tetragonal distortion. The optical absorption spectra of all the glass samples show a single broad band, which has been assigned to the ²B_1g→²B_2g transition of Cu²⁺ ions. The optical band gap energy (E_opt) and Urbach energy (ΔE) are calculated from their ultraviolet absorption edges. The emission bands observed in the ultraviolet and blue region are attributed to 3d⁹4s→3d¹⁰ triplet transition in Cu⁺ ion. The FT-IR spectra show that the glass system contains BO₃, BO₄ and PO₄ structural units.     

First principles study of structural, elastic, electronic and optical properties of the cubic perovskite BaHfO3

First principles study of structural, elastic, electronic and optical properties of the cubic perovskite-type BaHfO₃ has been reported using the pseudo-potential plane wave method within the local density approximation. The calculated equilibrium lattice is in a reasonable agreement with the available experimental data. The elastic constants and their pressure dependence are calculated using the static finite strain technique. A linear pressure dependence of the elastic stiffnesses is found. Band structures show that BaHfO₃ is a direct band gap between the occupied O 2p and unoccupied Hf d states. The variation of the gap versus pressure is well fitted to a quadratic function. Furthermore, in order to understand the optical properties of BaHfO₃, the dielectric function, absorption coefficient, optical reflectivity, refractive index, extinction coefficient, and electron energy loss are calculated for radiation up to 30 eV. We have found that O 2p states and Hf 5d states play a major role in the optical transitions as initial and final states, respectively. This is the first quantitative theoretical prediction of the elastic, electronic and optical properties of BaHfO₃ compound, and it still awaits experimental confirmation.     

Microstructure parameters and optical properties of cadmium ferrite thin films of variable thickness

CdFe₂O₄ thin films of different thicknesses were deposited onto glass substrates by the thermal evaporation technique. Their structural characteristics were studied by X-ray diffraction (XRD). The microstructure parameters, crystallite size, and microstrain were calculated. It is observed that both the crystallite size increases and microstrain increase with increasing with the film thickness. The fundamental optical parameters like absorption coefficient and optical band gap are calculated in the strong absorption region of transmittance and reflectance spectrum. The refractive indices have been evaluated in terms of the envelope method, which has been suggested by Swanepoel in the transparent region. The refractive index can be extrapolated by the Cauchy dispersion relationship over the whole spectra range, which extended from 400 to 2500 nm. The refractive index, n, increases on increasing the film thickness up to 733 nm and the variation of n with higher thickness lies within the experimental errors.     

Physical,optical and electrical properties of calcium bismuth borate glasses

The variation in physical, optical and electrical properties has been investigated as a function of Bi₂O₃ content in 20CaO?·?xBi₂O₃?·?(80???x)B₂O₃ (0?≤?x?≤?60, in mol%) glasses. The samples were prepared by normal melt-quenching process, and the optical absorption and reflection spectra were recorded in the wavelength range of 400–950 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The optical band gap, E _g, for indirect allowed and indirect forbidden transitions has been determined from the available theories and its value lies between 1.80–2.37 eV and 1.08–2.19 eV, respectively. The theoretical fitting of the optical absorption indicates that the present glass system behaves as an indirect gap semiconductor. The origin of the Urbach energy, ΔE, has been associated with the phonon-assisted indirect transitions. The refractive index and optical dielectric constant have been evaluated from the reflection spectra. The density and molar volume are found to depend on the molar concentration of Bi₂O₃. The values of DC electrical conductivity have been measured from 373 to 623 K and the activation energy has been calculated. Theoretical optical basicity has been reported as a function of the Bi₂O₃ content. The variations have been discussed in terms of structural changes.     

Optical absorption in boron clusters B6 and B 6 + : a first principles configuration interaction singles approach

The linear optical absorption spectra in neutral boron cluster B₆ and cationic B₆ ⁺ are calculated using a first principles correlated electron approach. The geometries of several low-lying isomers of these clusters were optimized at the coupled-cluster singles doubles (CCSD) level of theory. With these optimized ground-state geometries, excited states of different isomers were computed using the configuration-interaction singles (CIS) approach. The many-body wavefunctions of various excited states have been analyzed and the nature of optical excitation involved are found to be of collective, plasmonic type. We also benchmark our CIS results against more sophisticated equation-of-motion (EOM) CCSD approach for a few isomers.     

Thermally and optically induced effects on sub-band gap absorption in nanocrystalline CdSe (nc-CdSe) thin films

Nanocrystalline cadmium selenide (nc-CdSe) thin films have been prepared by thermal evaporation using the inert gas condensation (IGC) technique. Transmission electron microscopy (TEM) studies show that the CdSe nanocrystals (NCs) are spherical in shape. Constant photocurrent method (CPM) is used to determine the value of absorption coefficient in low absorption region of as-deposited, annealed and light soaked nc-CdSe thin films. Values of optical band gap (E_g) have been determined by using Tauc's relation for as-deposited, annealed and light soaked nc-CdSe thin films from the α values evaluated from reflection and transmission measurements. We have used a derivative procedure to sub-gap absorption spectra in order to get information on the energetic distribution of the occupied density of states below Fermi level. Constants such as optical gap E_g, Urbach edge E_u have been obtained from CPM spectra in as-deposited, annealed and light soaked nc-CdSe thin films. Concentration of defect states has also been calculated in as-deposited, annealed and light soaked nc-CdSe thin films.     

Effect of copper and cobalt impurities on the electronic structure and optical spectra of the intermetallic compound PrNi5

The electronic structure and optical properties of the intermetallic compound PrNi₅ and their evolution during the substitution of copper or cobalt atoms for nickel atoms have been investigated. The band spectra of the studied compounds have been calculated in the local spin density approximation corrected to account for strong electron-electron interactions in the 4f shell of the rare-earth ion (LSDA + U method). The dispersion relations of the optical conductivity in the interband light absorption region have been interpreted using the results of calculations of the electron density of states.     

Production, isolation, and characterization of group-2 metal-containing endohedral metallofullerenes

80 , Ca/Sr/Ba@C₈₂, Ca/Sr/Ba@C₈₄) are investigated for the first time by UV-Vis-NIR absorption spectroscopy and high-resolution ¹³C NMR. Direct evidence of the endohedral nature and cage structures are revealed by these measurements. Furthermore, we have found that each metallofullerene has 2–4 structural isomers, which have been isolated by multistage high-performance liquid chromatography. These isomers have different cage structures and give characteristic UV-Vis-NIR absorption spectra. Received: 22 September 1997/Accepted: 16 October 1997     

First-principles calculations of structural, electronic, optical and elastic properties of magnesite MgCO3 and calcite CaCO3

Detailed ab initio calculations of the structural, electronic, optical and elastic properties of two crystals - magnesite (MgCO₃) and calcite (CaCO₃) - are reported in the present paper. Both compounds are important natural minerals, playing an important role in the carbon dioxide cycling. The optimized crystal structures, band gaps, density of states diagrams, elastic constants, optical absorption spectra and refractive indexes dependence on the wavelength all have been calculated and compared, when available, with literature data. Both crystals are indirect band compounds, with calculated band gaps of 5.08 eV for MgCO₃ and 5.023 eV for CaCO₃. Both values are underestimated by approximately 1.0 eV with respect to the experimental data. Although both crystals have the same structure, substitution of Mg by Ca ions leads to certain differences, which manifest themselves in noticeable change in the electronic bands profiles and widths, shape of the calculated absorption spectra, and values of the elastic constants. Response of both crystals to the applied hydrostatic pressure was analyzed in the pressure range of phase stability, variations of the lattice parameters and characteristic interionic distances were considered. The obtained dependencies of lattice constants and calculated band gap on pressure can be used for prediction of properties of these two hosts at elevated pressures that occur in the Earth's mantle.     

Influence of doping of mercury atom(s) on optoelectronic properties of binary cadmium chalcogenides - A density functional theory based investigation with different exchange-correlation functionals and including spin-orbit coupling

Influence of doping of mercury atom(s) on optoelectronic properties of binary cadmium chalcogenides have been investigated theoretically by designing the mercury doped cadmium chalcogenide ternary alloys in B3 phase at some specific Hg-concentrations and studying their optoelectronic properties using DFT based FP-LAPW methodology. The structural properties are computed using WC-GGA, while spin-orbit coupling included electronic and optical properties are computed using TB-mBJ, EV-GGA, B3LYP and WC-GGA exchange-correlation functionals. In addition, electronic properties of mercury chalcogenides are calculated precisely using the GGA+U functionals. The concentration dependence of lattice parameter and bulk modulus of each of the Hg_xCd_1−xS, Hg_xCd_1−xSe, Hg_xCd_1−xTe alloy systems show almost linearity. For each of the alloy systems, band gap decreases almost linearly with increase in Hg-concentration in the unit cell and contribution from charge exchange to the band gap bowing is larger than that from for each of the volume deformation and structural relaxation. Also, covalent bonding exists between different constituent atoms in each compound. Optical properties of each specimen are computed from their spectra of dielectric function, refractive index, extinction coefficient, normal incidence reflectivity, optical conductivity, optical absorption coefficient and energy loss function. Several calculated results have been compared with available experimental and other theoretical data.