The effects of plastic deformation on band gap, electronic defect states and lattice vibrations of rutile

The extensive polygonization of 200 nm rutile crystals in high-energy dry milling allowed to study the spectral properties of grain boundaries and adjacent microstrained crystalline matter. Changes in UV, VIS, NIR, IR and FIR spectra during milling were followed. For the UV absorption edge the value of unstrained rutile was retained while residual traces of anatase, intergrown with the rutile phase, continued to act as traps for photoinduced charges. The evolving broad absorption in VIS and NIR could be attributed to electrons weakly bound to defects in the packing of oxygen anions at the grain boundaries, which may relax to face-sharing Ti³⁺-O octahedra. Among the IR-active lattice vibrations, the narrow E_u⁽²⁾ band showed a shift to higher frequencies by 15 cm⁻¹ which is definitively not due to phonon confinement or Fröhlich surface modes but probably to coupling of the bulk phonon to a plasmon at the grain boundary. At the external surface of the polygonized primary particle, the regular atomic order is destroyed by milling so that hydroxylation is replaced by physisorption of H₂O, as shown by IR and TG.     

EPR parameters and defect structures of the off-center Ti ion on the Sr site in neutron-irradiated SrTiO3 crystal

The EPR parameters (g factors and hyperfine structure constants A) for the tetragonal Ti³⁺ center in cubic phase and the rhombic Ti³⁺ center in tetragonal phase in the neutron-irradiated SrTiO₃ crystals are calculated from the third-order perturbation formulas of EPR parameters for d¹ ions. These low-symmetry Ti³⁺ centers in both phases of SrTiO₃ are due to the Ti³⁺ ion at “off center” on the Sr²⁺ site. From the calculation, the defect models (including the direction and magnitude of the Ti³⁺ off-center displacement) of the two Ti³⁺ centers in SrTiO₃ are estimated and the EPR parameters of both Ti³⁺ centers are reasonably explained on the basis of the defect models. The results are discussed.     

超越SNOM探针通光孔径尺寸的金属纳米间隙超分辨测量

采用电磁场有限元方法,数值模拟了孔径型扫描近场光学显微镜(aperture Scanning Near-field Optical Microscopy,a-SNOM)在照明模式下的工作过程.针对金偶极天线结构,改变天线长度和纳米间隙尺寸,计算了a-SNOM探针孔径的远场辐射速率随探针端面中心坐标变化的扫描曲线,实现了超越a-SNOM探针通光孔径尺寸的天线金属纳米间隙的超分辨测量,对于100nm通光孔径的探针,可分辨最小尺寸为10nm(0.016倍波长)的金属间隙.通过对比金属和介质偶极天线的a-SNOM探针远场辐射速率测量的计算结果,表明天线金属纳米间隙的超分辨测量的实现是由于金属间隙表面等离激元的激发.     

Theoretical study of low-lying electronic states and emission spectra of the excimer ions NaHe and NaNe

Ab initio CASSCF calculations using the Gaussian basis set aug_cc_pVTZ developed by Dunning et al. specifically for calculations at the post-HF level was carried out for excimer NaHe⁺ and NaNe⁺ ions in order to determine spectroscopic characteristics and radiation lifetimes of their low-lying excited electronic states. The computed emission spectra of these were shown to be in good agreement with the experimental ones observed recently by Hammer et al. (Hyperfine Interactions 88 (1994) 151). Contrary to the earlier popular opinion, all excited electronic states of these ions, correlating with the limit Rg⁺+Na, and not just the radiating singlet states turn out to be bound. It was shown that under the conditions of an experiment similar to the one performed by Hammer et al., the excited triplet NaHe⁺(1³Σ⁺) states can decay as a result of their interactions with a high-energy Ar⁺ beam. This decay has to be accompanied with the formation of the ions He⁺, which in turn can interact with sodium atoms to yield the radiating NaHe⁺(2¹Σ⁺) states again and, thus to maintain the emission observed in the experiment.     

Study on the impact of polar stratospheric clouds on high resolution mid-IR limb emission spectra

Satellite observations of polar stratospheric clouds (PSCs) in the mid-infrared by high resolution limb emission spectrometers like the Michelson Interferometer for Passive Atmospheric Sounding have been simulated. For particles with radius the scattered tropospheric radiance accounts for a significant part of the continuum signal and leads to absorption line features overlaid over the stratospheric emission spectrum. The scattered radiance shows a strong dependence on particle size up to about radius with a maximum around 3-4. The contribution of scattered radiation depends heavily on tropospheric cloud coverage and earth surface temperature. Distinction of PSCs of different composition is possible for small particles due to differences in the imaginary part of the refractive index. For particles with radii between 1 and the simulated spectra for various PSC compositions differ due to different real parts of the refractive index. For larger particles no distinction is possible any more. Solar radiance scattered by PSCs is important for wavenumbers larger than about . For a forward scattering geometry with 30° between the position of the sun and the limb viewing direction solar contribution exceeds the terrestrial scattered radiation by about a factor of 10.     

Evaluation of quadrature schemes for the discrete ordinates method

After reviewing the presently available quadrature schemes for the discrete ordinates method, the accuracy of different schemes is analyzed and evaluated. It is shown from a comprehensive error analysis that the moment conditions have to satisfied not only for the principal coordinates directions, as it is mostly carried out, but for any arbitrary test direction. Among the schemes with approximately 50 discrete ordinates the DCT-020-2468 quadrature was found to give the best accuracy. The highest accuracy among all schemes is achieved by the LC-11 quadrature which requires 96 discrete ordinates. This scheme is rarely used up to date and deserves more attention for high accuracy predictions.     

Radiation heat transfer in axisymmetric quartz glass tubes

A mathematical model is proposed to describe the heat transfer in quartz glass axisymmetric tubes. Heat is transferred inside the glass by radiation and conduction. Scattering of thermal radiation inside the glass is ignored. At the boundaries of the tube the radiative intensity is specularly reflected. The spectral dependent radiative intensity and the temperature distribution inside the tube are determined. The model is applied to simulate the cooling process of a quartz glass tube. The calculated temperature is in agreement with that obtained from an experiment. Furthermore, steady-state temperature distributions in quartz glass tubes of different lengths have been determined.     

Computer simulation, thermodynamic and microstructural studies of benzamide–benzoic acid eutectic system

Phase diagram of benzamide–benzoic acid system has been studied by the thaw–melt method. Linear velocities of crystallization of the components and the eutectic mixture were determined at different undercoolings. Values of the heat of fusion were obtained from DSC studies. Excess Gibbs free energy, excess enthalpy and excess entropy of mixing were calculated. In order to know the nature of interaction between the two components, FT-IR spectral analyses were done. In addition to these studies, computer simulation has been done to obtain an idea about the interaction energy and the optimized geometry of the eutectic mixture. Microstructural studies showed the formation of an irregular structure in the eutectic mixture, which changed with aging and on addition of impurities.     

Decay kinetics of the green emission in tungstates and molybdates

Luminescence characteristics of a number of undoped and variously doped PbWO₄ crystals were studied at 0.4–400 K by the time-resolved spectroscopy and compared with those of ZnWO₄,CdWO₄ and PbMoO₄ crystals. Two types of green emission centres are detected in PbWO₄ crystals. The centres of the first type are responsible for the low-temperature 2.3–2.4 eV emission observed under excitation around 3.90–3.95 eV. The structure and parameters of their relaxed excited states were determined. It was concluded that the origin of defects responsible for the green emission of the first type could vary for different crystals. The centres of the second type with the emission around 2.5 eV appear in crystals containing oxygen vacancies after the thermal destruction of Pb⁺-WO₃ centres at T>180 K. Decomposition of the exciton and various defect-related states was also studied, and activation energies of this process were calculated.