Nano-sized blue spectral shift in sol–gel derived mesoporous titania films

Following the spectral energy shift of the energy gap (blue shift) of the TiO₂ sol–gel derived films we have evaluated diameters of the nanocrystallites. The TiO₂ films were deposited by dip-coating technique. Two types of mesoporous films were studied: films with porosity ~16% and refractive index (2.15 at wavelength 633 nm) and films with porosity ~46% and refractive index (1.61 at wavelength 633 nm). High porosity and consequently low refractive index was achieved by adding the non-ionic surfactant Triton X-100 to the starting solution as template. The principal goal of the work is to establish the influence of the Triton X-100 on the morphology as well as to establish a possible correlation between the morphology and optical features of the titania films. The surface morphology was explored using AFM method. And the energy gap was determined from the transmission spectra. Analysis of the blue energy spectral shift is performed following the excitonic model.     

Correlation between the real Co particle size distributions and the magnetic properties of GMR Cu–10Co alloy

The results of transmission electron microscopy (TEM), magnetic and magneto-resistivity investigations of the Cu–10Co (wt%) giant magneto-resistance (GMR) melt-spun ribbons are reported and discussed. To obtain different distributions of ferromagnetic Co particles in a non-magnetic Cu matrix, the alloy was aged at 550 °C for 0.5, 1, 2, 16, and 32 h. Particle size measurements were performed using quantitative TEM metallography methods. Two size classes of Co particles are identified: primary particles (P) precipitated during the melt-spinning process and the secondary particles (S) precipitated during the ageing process. The results of magnetization and coercitivity are correlated with the results of calculations based on the real Co particle distributions determined from TEM micrographs. The behavior of magnetization and coercive force in function of ageing time is explained as related with changes of a mean particle size. It is shown that the GMR effect is not influenced by Co particles distribution for the S particles with the mean size less than 10 nm, whereas for Co distributions with larger mean diameters, the GMR effect is strongly reduced.     

Crystal field in RPdIn (R=Ce, Pr, Nd) compounds

The RPdIn compounds (R = rare earth) crystallise in the hexagonal ZrNiAl-type crystal structure. The compounds from this family exhibit a great variety of interesting magnetic properties including heavy fermion behaviour. In order to get a deeper insight into nature of magnetism of RPdIn with light rare earths elements (La–Nd) an inelastic neutron scattering experiment was performed. For compounds with Pr and Nd excitations due to crystal field were clearly distinguished. On the other hand, interesting behaviour for the CePdIn sample was observed. The sample exhibits no signs of crystal field excitations, likely due to highly delocalised Ce 4f states leading to its heavy fermion behaviour.     

Molecular dynamics modeling in quantum chemical calculations. Optical absorption spectra of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline derivatives

Paper presents the quantum chemical modeling of the optical absorption spectra of 6-fluoro, 6-bromo, 7-trifluoromethyl, 6-cyano and 6-carboethoxy derivatives of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) in combination with molecular dynamics (MD) simulations at T=300 K. It is shown that a particular rotational dynamics of the methyl, trifluoromethyl or ethyl groups practically does not influence the optical absorption in the spectral range 200-500 nm whereas broadening of absorption bands may be well reproduced within MD simulations including all types of nuclei vibrations. The results of calculations are compared with the measured spectra of optical absorption. The quantum chemical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of the first absorption band (absorption threshold).     

Acousto-optic lens for pulsed lasers

Theoretical predictions of the acousto-optic interaction under Raman-Nath conditions of ultrasound and laser light with a beam width w comparable to or smaller than the ultrasonic wavelength lambda are experimentally investigated, and good agreement between experiment and prediction is found. The experimental setup consists of a pulsed laser, emitting pulses that are synchronized with the sound frequency by means of a controllable delay time. When w approximately lambda, strong focusing is obtained for most delay times. The lensing properties of this configuration are carefully investigated.     

Diffraction of light by two ultrasonic beams of frequency ratio 1:2, beyond the Raman-Nath diffraction regime

Light diffraction by two ultrasonic waves of frequency ratio 1:2 is examined beyond the Raman-Nath diffraction regime. Measurements were taken of +/- 1 order diffracted light intensities for some Raman-Nath parameter values, as a function of the phase shift between the sound beams. The experimental results obtained are discussed and compared with relevant theoretical predictions. Within the experimental conditions, a quite good quantitative agreement between the experimental data and the appropriate theoretical expectations is observed.     

Optical absorption of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline derivatives: Molecular dynamics modeling

Paper deals with quantum chemical modeling of the optical absorption spectra of 6-fluoro, 7-trifluoromethyl, 6-cyano, 6-carboethoxy and 6-tert-butyl derivatives of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) applied to the equilibrium molecular conformation in vacuo (T = 0 K) or molecular dynamic (MD) trajectories as obtained within fragmental or total MD simulations at T = 300 K. The results of these calculations are compared with the measured spectra of optical absorption. The quantum chemical analysis show that the dynamics of the methyl, trifluoromethyl, carboethoxy and tert-butyl groups practically does not influence the absorption spectra whereas the strongest their modifications are found to be related with dynamics of the aromatic group. The semiempirical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of absorption bands. In most cases the quantum chemical calculations describe properly the trends of their changes depending on the lateral substituent.     

Electronic structure and magnetism of RPdIn compounds (R=La, Ce, Pr, Nd)

RPdIn (R = La-Nd) compounds were studied by means of magnetic susceptibility, specific heat and photoelectron spectroscopy measurements. The results prove that CePdIn is an antiferromagnetic Kondo lattice with T_N below 1.7 K. The Pr-based indide remains paramagnetic down to 1.7 K, and the lack of any magnetic ordering may be due to the presence of a singlet as the crystalline electric field ground state or/and strong hybridization between Pr 4f states and Pd 4d states. In turn, NdPdIn exhibits ferromagnetism below about 26 K. In contrast to CePdIn, for the Pr- and Nd-based compounds any significant enhancement of the electronic specific heat coefficient was observed.     

Magnetic and thermodynamic properties of NdT2Ge2 (T=Pd, Ag) compounds

Physical properties of NdPd₂Ge₂ and NdAg₂Ge₂, crystallizing with the tetragonal ThCr₂Si₂-type crystal structure, were investigated by means of magnetic, calorimetric, electrical transport as well as by neutron diffraction measurements. The specific heat studies and neutron diffraction measurements were performed down to 0.30 K and 0.47 K, respectively. Both compounds exhibit antiferromagnetic ordering below T_N equal to 1.5 K for NdPd₂Ge₂ and 1.8 K for NdAg₂Ge₂. Neutron diffraction data for the latter germanide indicate antiferromagnetic collinear structure described by the propagation vector k=(0.5, 0, 0.5). The Nd magnetic moments equal to 2.24(5) μ_B at 0.47 K are aligned along the a-axis and have the +− sequence within the crystal unit cell. For NdPd₂Ge₂ only very small Bragg peaks of magnetic origin were observed in the neutron diffraction patterns measured below T_N, thus hampering determination of the magnetic structure. Both compounds exhibit metallic-like electrical conduction. From the specific heat data the crystal electric field (CEF) levels schemes were determined. Difference between the overall CEF splitting in the two compounds is correlated with their structural parameters.     

Optical poling effect and optical absorption of cyan, ethylcarboxyl and tert-buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline: experiment and quantum-chemical simulations

We present here results of experimental studies and quantum-chemical simulations of optical absorption and optical poling effects performed on a new synthesized cyan, ethylcarboxyl and tert-buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline incorporated into polymer matrix or dissolved in organic solutions. The efficiency of second-order optical susceptibility d vs photoinduced power density I(p) clearly saturates to certain magnitude d(eff) at sufficient power densities (I(p) > or = 1.3 GW cm(-2)). Comparing experimental data and results of semiempirical quantum-chemical simulations one can conclude that there exists generally a good correlation between the magnitude of saturated susceptibilities d(eff) and macroscopic hyperpolarizabilities for all compounds except the chromophore 1,3-dimethyl-6-cyano-[PQ] only. The discrepancy for this compound may reflect a specific contribution of surrounding polymer matrix. According to the quantum chemical analysis the methyl-containing cyan and ethylocarcoxyl derivatives reveal four/five strong absorption bands in the spectral range 200-500 nm. A substitution of the methyl groups by the phenyl group causes the substantial changes of the absorption spectra mainly in the spectral range 240-370 nm. Measured and calculated absorption spectra manifest rather good agreement mainly in the part regarding the spectral positions of the first oscillator (absorption threshold). The quantum-chemical PM3 method shows the best agreement with experiment. At the same time a considerable broadening almost of all absorption bands appears as a characteristic feature of all measured spectra. The discrepancies between the calculated and the measured spectra are attributed to electron-vibronic coupling as well as to a specific rotational dynamics of phenyl rings.