Optical properties of chromium-doped fluoroindate glasses

This work reports on the optical properties of Cr3+ ions in the pseudoternary system InF3-GdF3-GaF3. Linear properties, investigated through absorption and emission spectra, provide information on the crystal field, the frequency, and number of phonons emitted during the absorption to the 4T2 band and the emission to the 4A2 ground state, and the Fano antiresonance line shape in the vicinity of the 4A2→2E transition. A study of the nonlinear refractive index as a function of the wavelength, carried out with the Z-scan technique, provides spectroscopic data about electronic transitions starting from the excited state.

Generalized simulated annealing: Application to silicon clusters

We have compared the recently introduced generalized simulated annealing (GSA) with conventional simulated annealing (CSA). GSA was tested as a tool to obtain the ground-state geometry of molecules. We have used selected silicon clusters (Sin, n=4-7,10) as test cases. Total energies were calculated through tight-binding molecular dynamics. We have found that the replacement of Boltzmann statistics (CSA) by Tsallis's statistics (GSA) has the potential to speed up optimizations with no loss of accuracy. Next, we applied the GSA method to study the ground-state geometry of a 20-atom silicon cluster. We found an original geometry, apparently lower in energy than those previously described in the literature.

Thermally activated dynamics of the tilts of the CuO6 octahedra, hopping of interstitial O, and possible instability towards the LTT phase in La2CuO4+δ

The anelastic spectrum (dynamic Young's modulus and elastic energy absorption) of La2CuO4+δ has been measured between 1 and 700 K with 0<δ<0.02. The spectrum of stoichiometric La2CuO4 in the low-temperature orthorhombic (LTO) phase is dominated by two intense relaxation processes which cause softenings of 16% around 150 K and 9% below 30 K at f∼1 kHz. The relaxation at 150 K is attributed to the presence of a fraction of the CuO6 octahedra which are able to change their tilted configuration by thermal activation between orientations which are nearly energetically equivalent, possibly within the twin boundaries. The relaxation below 30 K is governed by tunneling, and involves a considerable fraction of the lattice atoms. It is proposed that the double-well potentials for the low-temperature relaxation are created by the tendency of the LTO phase to form low-temperature tetragonal (LTT) domains, which however are not stabilized like when La is partially substituted with Ba. On doping with excess O, the relaxation rates of these processes are initially enhanced by hole doping, while their intensities are depressed by lattice disorder; an explanation of this behavior is provided. Excess O also causes two additional relaxation processes. The one appearing at lower values of δ is attributed to the hopping of single interstitial O2- ions, with a hopping rate equal to τ-1=2×10-14exp(-5600/T) s. The second process is slower and can be due to O pairs or other complexes containing excess O.

Influence of nearest-neighbor Coulomb interactions on the phase diagram of the ferromagnetic Kondo model

The influence of a nearest-neighbor Coulomb repulsion of strength V on the properties of the ferromagnetic Kondo model is analyzed using computational techniques. The Hamiltonian studied here is defined on a chain using localized S = 1/2 spins, and one orbital per site. Special emphasis is given to the influence of the Coulomb repulsion on the regions of phase separation recently discovered in this family of models, as well as on the double-exchange-induced ferromagnetic ground state. When phase separation dominates at V= 0, the Coulomb interaction breaks the large domains of the two competing phases into small islands of one phase embedded into the other. This is in agreement with several experimental results, as discussed in the text. Vestiges of the original phase separation regime are found in the spin structure factor as incommensurate peaks, even at large values of V. In the ferromagnetic regime close to density n = 0.5, the Coulomb interaction induces tendencies to charge ordering without altering the fully polarized character of the state. This regime of charge-ordered ferromagnetism may be related with experimental observations of a similar phase by Chen and Cheong [Phys. Rev. Lett. 76, 4042 (1996)]. Our results reinforce the recently introduced notion [see, e.g., S. Yunoki et al., Phys. Rev. Lett. 80, 845 (1998)] that in realistic models for manganites analyzed with unbiased many-body techniques, the ground state properties arise from a competition between ferromagnetism and phase-separation - charge-ordering tendencies. ©1999 The American Physical Society.

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Magneto-optical studies of the correlation between interface microroughness parameters and the photoluminescence line shape in GaAs/Ga0.7Al0.3As quantum wells

In this work we analyze the relation between the interface microroughness and the full width at half maximum (FWHM) of the photoluminescence (PL) spectra for a GaAs/Ga0.7Al0.3As multiple quantum well (QW) system. We show that, in spite of the complex correlation between the microscopic interface-defects parameters and the QW optical properties, the Singh and Bajaj model [Appl. Phys. Lett. 44, 805 (1984)] provides a good quantitative description of the excitonic PL-FWHM. ©1999 The American Physical Society.

Pressure-induced phase transitions in Zr-rich PbZr1-xTixO3 ceramics

A Raman study of structural changes in the Zr-rich PbZr1-x TixO3 (PZT) system under hydrostatic pressures up to 5.0 GPa is presented. We observe that externally applied pressure induces several phase transitions in PZT ceramics among phases with orthorhombic (Ao), rhombohedral low-temperature (RLT), and rhombohedral high-temperature (RHT) symmetries (all found in PZT at ambient pressure and room temperature). Each of the compositions investigated (0.02 ≤ x ≤ 0.14) exhibits a high-pressure phase with orthorhombic (OI′) symmetry. We further report a detailed study of the pressure dependence of Raman frequencies to elucidate the phase transitions and to provide a set of pressure coefficients for the high-pressure phases.

Comment on Time-reversal symmetry-breaking superconductivity

It is pointed out that erroneous Bardeen-Cooper-Schrieffer model equations have been used by Haranath Ghosh in his recent treatment of time-reversal symmetry-breaking superconductivity. Consequently, his numerical results are misleading, and his conclusions are not to the point.

The two-impurity Anderson model: An effective medium approach

The two-impurity Anderson model is solved within a effective medium approach. All impurity parameters are modelled via Slater atomic orbitals. Impurity spectral densities and spin correlation functions are readily computed. Results are presented for the zero temperature, half-filled case. © 2002 Elsevier Science B.V. All rights reserved.

Spectroscopic characteristics of Er3+ in the two crystallographic sites of Gd2SiO5

Gd2SiO5 is among the interesting and suitable hosts for Er3+ which find extensive applications in the infrared, visible and ultraviolet spectral regions. In order to investigate its potentialities, a prior study of the spectroscopic behaviour of Er3+ substituting for Gd3+ ions in the two crystallographic sites of the host was performed. Absorption, excitation, site-selective emission and time-resolved spectroscopies were employed in the visible spectral region to study transitions between excited 4S3/2 and ground 4I15/2 states. These levels multiplets were attributed to each site separately, and their corresponding 4S3/2 lifetimes (1.8 ± 0.1 μs for site 1 and 3.2 ± 0.1 μs for site 2) were determined.

Multiperiodic magnetic structures in Hubbard superlattices

We consider fermions in one-dimensional superlattices (SL's), modeled by site-dependent Hubbard-U couplings arranged in a repeated pattern of repulsive (i.e., U>0) and free (U=0) sites. Density matrix renormalization group diagonalization of finite systems is used to calculate the local moment and the magnetic structure factor in the ground state. We have found four regimes for magnetic behavior: uniform local moments forming a spin-density wave (SDW), floppy local moments with short-ranged correlations, local moments on repulsive sites forming long-period SDW's superimposed with short-ranged correlations, and local moments on repulsive sites solely with long-period SDW's; the boundaries between these regimes depend on the range of electronic densities ρ and on the SL aspect ratio. Above a critical electronic density, ρ↑↓, the SDW period oscillates both with ρ and with the spacer thickness. The former oscillation allows one to reproduce all SDW wave vectors within a small range of electronic densities, unlike the homogeneous system. The latter oscillation is related to the exchange oscillation observed in magnetic multilayers. A crossover between regimes of thin to thick layers has also been observed.

Raman scattering study of the PbZr1-xTixO3 system: Rhombohedral-monoclinic-tetragonal phase transitions

In this paper we present a Raman-scattering study of the phase transitions in the PbZr1-xTixO3 systems around the morphotropic phase boundary over a wide temperature range. The boundary between rhombohedral and monoclinic phases was found to be a quasivertical line between x = 0.46 and x = 0.47. We also studied the monoclinic-tetragonal phase boundary and our spectroscopic results agree very well with those reported by using x-ray diffraction.

Magnetic behavior of poly(3-methylthiophene): Metamagnetism and room-temperature weak ferromagnetism

A weak ferromagnetic phase is shown in pressed pellets of partially doped poly(3-methylthiophene) (P3MT) in the whole range from 1.8 to 300 K in magnetic measurements. Thermoremanence data have been used to estimate the suppression of this phase to be around 815 K. We also show that instead of the classical antiferromagnetism for the first-order interaction that gives weak ferromagnetism as a second-order effect, metamagnetic behavior is observed. X-band electron spin resonance (ESR) measurements and magnetization measurements allowed us to estimate that 8.1% of the total number of spins contributes to the weak ferromagnetism at room temperature. The doping level obtained from the ESR data is in good agreement with that estimated from electron dispersive spectroscopy measurements.

Structural study of aged saturated silica gels obtained from tetramethoxysilane sonohydrolysis with different water/tetramethoxysilane molar ratio

The structural characteristics of saturated silica sonogels were studied by means of small-angle x-ray scattering (SAXS) and thermogravimetric analysis (TG), after a long time of aging in saturated conditions. The sonogels were obtained by a sol-gel routine from ultrasound stimulated tetramethoxysilane (TMOS) hydrolysis carried out with the initial water/TMOS molar ratio (r) ranging from 2 to 10. The saturated sonogel structure can be described as composed by mass fractal-like aggregates (clusters) of primary silica particles, all imbibed in a liquid phase. The values of the mass fractal dimension (D) of the clusters was found all around 2.5, while the characteristic size of the clusters (ξ) was found generally increasing with r, going from approximately 2.3 nm (r = 2) to 4.5 nm (r = 10). The volume fraction of the clusters was estimated from the SAXS data. The results were compared to the values of weight loss fraction at the inflection point that has been found in the derivative of the TG curve, which should accounts for the instant in which the meniscus of the liquid phase penetrates into the clusters under a rapid evaporation process as in a TG test.

Comparative study using small-angle x-ray scattering and nitrogen adsorption in the characterization of silica xerogels and aerogels

A comparative study using small-angle x-ray scattering (SAXS) and nitrogen adsorption has been carried out in the structural characterization of silica xerogels and aerogels, obtained from tetraethoxysilane sonohydrolysis. The specific surface and the mean pore size as measured by both the techniques were found to be in notable agreement in all cases for aerogels and xerogels. According to the SAXS data, aerogels at 500 °C exhibit a mass fractal structure with fractal dimension D∼2.4 in the range between the correlation length ξ∼5.3 nm and a∼0.75 nm. An experimental method to probe the mass fractal structure of aerogels from exclusively nitrogen adsorption isotherms has been presented. For aerogels at 500 °C, we have found D∼2.4 in the range between the pore width 2rξ∼33 nm and 2ra∼4.5 nm, which is in notable agreement with the SAXS results (D ∼2.4, ξ∼5.3 nm, a∼0.75 nm) if we assign the pore width 2r probed by the Kelvin equation in the adsorption method to the Bragg distance 2π/q associated to the correlation length 1/q probed by SAXS.