Resonant excitation energy transfer in [Rh(bpy)3][NaCr(ox)3]ClO4

Resonant fluorescence line narrowing of the R1 line of the [Cr(ox)3]3− chromophore in [Rh(bpy)3][NaCr(ox)3]ClO4 at 1.6 K neither gives rise to the usual three-line pattern nor to spectral diffusion. Instead multi-line spectra with spacings equal to the zero-field splitting of the ground state are observed. This phenomenon is attributed to efficient non-radiative resonant energy transfer within the R1 line.

Nitrenes, diradicals, and ylides. Ring expansion and ring opening in 2-quinazolylnitrenes

Tetrazolo[1,5-a] quinazoline (9) is converted to 2-azidoquinazoline (10) on sublimation at 200 degrees C and above, and the azide-tetrazole equilibrium is governed by entropy. 2-Quinazolylnitrenes 11 and 27 and/ or their ring expansion products 14 and 29 can undergo type I (ylidic) and type II (diradicaloid) ring opening. Argon matrix photolysis of 9/10 affords 2-quinazolylnitrene (11), which has been characterized by ESR, UV, and IR spectroscopy. A minor amount of a second nitrene, formed by rearrangement or ring opening, is also observed. A diradical (19) is formed rapidly by type II ring opening and characterized by ESR spectroscopy; it decays thermally at 15 K with a half-life of ca. 47 min, in agreement with its calculated facile intersystem crossing (19T -> 19OSS) followed by facile cyclization/rearrangement to 1-cyanoindazole (21) (calculated activation barrier 1- 2 kcal/mol) and N-cyanoanthranilonitrile (22). 21 and 22 are the isolated end products of photolysis. 21 is also the end product of flash vacuum thermolysis. An excellent linear correlation between the zero-field splitting parameter D (cm(-1)) and the spin density F on the nitrene N calculated at the B3LYP/EPRIII level is reported (R-2 = 0.993 for over 100 nitrenes). Matrix photolysis of 3-phenyltetrazolo[1,5-a] quinazoline (25) affords the benzotriazacycloheptatetraene 29, which can be photochemically interconverted with the type I ring opening product 2-isocyano-alpha-diazo-alpha- phenyltoluene (33) as determined by IR and UV spectroscopy. The corresponding carbene 37, obtained by photolysis of 33, was detected by matrix ESR spectroscopy.

Spectroscopic analysis of terrestrial analogues for the interpretation of surface composition of rocky bodies in the solar system. Effects of mineral mixing and particle size. Applications to moon, mars and implications for mercury.

Among the Solar System’s bodies, Moon, Mercury and Mars are at present, or have been in the recent years, object of space missions aimed, among other topics, also at improving our knowledge about surface composition. Between the techniques to detect planet’s mineralogical composition, both from remote and close range platforms, visible and near-infrared reflectance (VNIR) spectroscopy is a powerful tool, because crystal field absorption bands are related to particular transitional metals in well-defined crystal structures, e.g., Fe2+ in M1 and M2 sites of olivine or pyroxene (Burns, 1993). Thanks to the improvements in the spectrometers onboard the recent missions, a more detailed interpretation of the planetary surfaces can now be delineated. However, quantitative interpretation of planetary surface mineralogy could not always be a simple task. In fact, several factors such as the mineral chemistry, the presence of different minerals that absorb in a narrow spectral range, the regolith with a variable particle size range, the space weathering, the atmosphere composition etc., act in unpredictable ways on the reflectance spectra on a planetary surface (Serventi et al., 2014). One method for the interpretation of reflectance spectra of unknown materials involves the study of a number of spectra acquired in the laboratory under different conditions, such as different mineral abundances or different particle sizes, in order to derive empirical trends. This is the methodology that has been followed in this PhD thesis: the single factors previously listed have been analyzed, creating, in the laboratory, a set of terrestrial analogues with well-defined composition and size. The aim of this work is to provide new tools and criteria to improve the knowledge of the composition of planetary surfaces. In particular, mixtures composed with different content and chemistry of plagioclase and mafic minerals have been spectroscopically analyzed at different particle sizes and with different mineral relative percentages. The reflectance spectra of each mixture have been analyzed both qualitatively (using the software ORIGIN®) and quantitatively applying the Modified Gaussian Model (MGM, Sunshine et al., 1990) algorithm. In particular, the spectral parameter variations of each absorption band have been evaluated versus the volumetric FeO% content in the PL phase and versus the PL modal abundance. This delineated calibration curves of composition vs. spectral parameters and allow implementation of spectral libraries. Furthermore, the trends derived from terrestrial analogues here analyzed and from analogues in the literature have been applied for the interpretation of hyperspectral images of both plagioclase-rich (Moon) and plagioclase-poor (Mars) bodies.

Magnetic susceptibility of Ce and Pr in SrB6 and YB6

Magnetic susceptibility data suggest that the crystal field splittings of the 4f levels of Ce and Pr impurities are larger in metallic YB6 than in isostructural and semiconducting SrB6, contrary to what might be expected. © 1969.

A new way of uniform splitting of the optical power by directional coupling between the photonic crystal waveguides

Directional coupler can be constructed by putting multiple photonic crystal waveguides together. The propagation of the optical field entering this system symmetrically was analysed numerically according to self-imaging principle. On the basis of this structure, ultracompact multiway beam splitter was designed and the ones with three and four output channels were discussed in details as examples. By simply tuning the effective refractive index of two dielectric rods in the coupler symmetrically to induce the redistribution of the power of the optical field, uniform or free splitting can be achieved. Compared with the reported results, this way is simpler, more feasible and more efficient and has extensive practical value in future photonic integrated circuits.

Crystal structure of quenched and in-field electroluminescent phosphors

Electroluminescent zinc sulfide doped with copper and chloride (ZnS:Cu, Cl) powder was heated to 400°C and rapidly quenched to room temperature. Comparison between the quenched and non-quenched phosphors using synchrotron radiation X-ray powder diffraction (XRPD) (λ = 0.828692 Å) and X-ray absorption spectroscopy (XAS) was made. XRPD shows that the expected highly faulted structure is observed with excellent resolution out to 150° 2θ (or to (12 2 2) of the sphalerite phase). The quenched sample compared to the unheated sample shows a large change in peak ratios between 46.7° and 46.9°, which is thought to correspond to the wurtzite (0 0 6), (0 3 2) and sphalerite (3 3 3)/(5 1 1) peaks. Hence, a large proportion of this sphalerite diffraction is lost from the material upon rapid quenching, but not when the material is allowed to cool slowly. The Zn K-edge XAS data indicate that the crystalline structures are indistinguishable using this technique, but do give an indication that the electronic structure has altered due to changing intensity of the white line. It is noted that the blue electroluminescence (EL) emission bands are lost upon quenching: however, a large amount of total EL emission intensity is also removed, which is consistent with our findings. We report the XRPD of a working alternating-current electroluminescence device in the synchrotron X-ray beam, which exhibits a new diffraction pattern when the device is powered in an AC field even though the phosphor is fixed in the binder. Significantly, only a few crystals are required to yield the diffraction data because of the high flux X-ray source. These in panel data show multiple sharp diffraction lines spread out under the region, where capillary data show broad diffraction intensity indicating that the phosphor powder is comprised of unique crystals, each having different structures.

DPIV and Interferometry Technique for Velocity Field and Concentration Fields Measurement in Crystal Growth

The property of crystal depends seriously on the solution concentration distribution near the growth surface of a crystal. However, the concentration distributions are affected by the diffusion and convection of the solution. In the present experiment, the two methods of optical measurement are used to obtained velocity field and concentration field of NaClO₃ solution. The convection patterns in sodium chlorate (NaClO₃) crystal growth are measured by Digital Particle image Velocimetry (DPIV) technology. The 2-dimentional velocity distributions in the solution of NaClO3 are obtained from experiments. And concentration field are obtained by a Mach-Zehnder interferometer with a phase shift servo system. Interference patterns were recorded directly by a computer via a CCD camera. The evolution of velocity field and concentration field from dissolution to crystallization are visualized clearly. The structures of velocity fields were compared with that of concentration field.

Effect of non-uniform magnetic field on crystal growth by floating-zone method in microgravity

The magnetic damping effect of the non-uniform magnetic field on the floating-zone crystal growth process in microgravity is studied by numerical simulation. The results show that the non-uniform magnetic field with designed configuration can effectively reduce the flow near the free surface and then in the melt zone. At the same time, the designed magnetic field can improve the impurity concentration non-uniformity along the solidification interface. The primary principles of the magnetic field configuration design are also discussed.

Magnetic field design for floating zone crystal growth

The magnetic fields produced by electrical coils are designed for P-doped Si crystal growth in a floating full zone in microgravity environment. The fields are designed specially to reduce the how near the free surface and then in the melt zone by adjusting the coil positions near the melt zone. The effects of the designed magnetic fields on reducing the Row velocity and the non-uniformity of the concentration distribution in the melt zone are better than those of the case of a uniform longitudinal magnetic field, obtained by numerical simulation. It is expected to improve the radial macro-segregation and reduce the convection in the crystal growth at the same time by using the designed magnetic field.

Reflection and transmission of Gaussian beam from a uniaxial crystal slab

We investigate the characteristics of Gaussian beams reflected and transmitted from a uniaxial crystal slab with an arbitrary orientation of its optical axis. The formulas of the total electric and magnetic fields inside and outside the slab are derived by use of Maxwell's equations and by matching the boundary conditions at the interfaces. Numerical simulations are presented and the field values as well as the power densities are computed. Negative refractions are demonstrated when the beam is transmitted through a uniaxial crystal slab. Beam splitting of the reflected beam is observed and is explained by the resonant transmission for plane waves. Dependences of the lateral shift on the incident angle and beam width are discussed. Negative and positive lateral shifts are observed due to the spatial anisotropic properties.

Investigation of effective internal field in congruent lithium niobate crystal by digital holographic interferometry

The phase contrast across the crystal thickness induced by the internal field is measured by the digital holographic interferometry just after the congruent lithium niobate crystal is partially poled. The direction of applied external field is antiparallel to that of internal field, and the measured phase contrast varies linearly with the applied external field. A new internal field is obtained by this method and named effective internal field. The distinct discrepancy between effective and equivalent internal fields is observed. The authors attribute this effect to the new macroscopic representation of elastic dipole components of defect complex in the crystal. (c) 2007 American Institute of Physics.

Electric-field switching of exciton spin splitting in coupled quantum dots

We investigate theoretically the spin splitting of the exciton states in semiconductor coupled quantum dots (CQDs) containing a single magnetic ion. We find that the spin splitting can be switched on/off in the CQDs via the sp-d exchange interaction using the electric field. An interesting bright-to-dark exciton transition can be found and it significantly affects the photoluminescence spectrum. This phenomenon is induced by the transition of the ground exciton state, arising from the hole mixing effect, between the bonding and antibonding states. (C) 2008 American Institute of Physics.

Electric Field Control of Interface Related Spin Splitting in Step Quantum Wells

Spin splitting of the AlyGa1-yAs/GaAs/AlxGa1-xAs/AlyGa1-yAs (x not equal y) step quantum wells (QWs) has been theoretically investigated with a model that includes both the interface and the external electric field contribution. The overall spin splitting is mainly determined by the interface contribution, which can be well manipulated by the external electric field. In the absence of the electric field, the Rashba effect exists due to the internal structure inversion asymmetry (SIA). The electric field can strengthen or suppress the internal SIA, resulting in an increase or decrease of the spin splitting. The step QW, which results in large spin splitting, has advantages in applications to spintronic devices compared with symmetrical and asymmetrical QWs. Due to the special structure design, the spin splitting does not change with the external electric field.

Experimental study of mode field evolution of dual-core photonic crystal fiber

The accurate mode field profile of high negative dispersion dual-core photonic crystal fiber (DCPCF) is measured. The mode field evolution of DCPCF with wavelength is studied experimentally for the first time. The measurement result shows that no individual inner core mode or outer core mode exists, but two modes coexist simultaneously, and either one of them is dominant. The mode field evolution versus wavelength indicates that the wavelength range where the modes coupling takes place between inner core and outer core is broader than that of theoretical design.

Zero-field spin splitting in In0.52Al0.48As/InxGa1-xAs metamorphic high-electron-mobility-transistor structures on GaAs substrates using Shubnikov-de Haas measurements

Shubnikov-de Haas measurements were carried out for In0.52Al0.48As/InxGa1-xAs metamorphic high-electron-mobility-transistor structures grown on GaAs substrates with different indium contents and/or different Si delta-doping concentrations. Zero-field (B-->0) spin splitting was found in samples with stronger conduction band bending in the InGaAs well. It was shown that the dominant spin splitting mechanism is attributed to the contribution by the Rashba term. We found that zero-field spin splitting not only occurs in the ground electron subband, but also in the first excited electron subband for a sample with Si delta-doping concentration of 6x10(12) cm(-2). We propose that this In0.52Al0.48As/InxGa1-xAs metamorphic high-electron-mobility-transistor structure grown on GaAs may be a promising candidate spin-polarized field-effect transistors. (C) 2002 American Institute of Physics.