I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

Absolute left-handed behaviors in a triangular elliptical-rod photonic crystal

In this paper we theoretically study the left-handed behaviors in a two-dimensional triangular photonic crystal made of elliptical rods in air. An absolute left-handed region is found in the second photonic band by using the plane wave expansion method to analyze the photonic band structure and equifrequency contours. Typical left-handed behaviors such as negative refraction, flat superlensing and plano-concave lensing are demonstrated by the finite-difference time-domain simulations. These behaviors are also compared with the quasi-negative refraction and the resulted focusing effects in a square-lattice two-dimensional photonic crystal. (c) 2005 Optical Society of America

Subwavelength imaging by a dielectric-tube photonic crystal

In contrast to previous two-dimensional coated photonic crystals, in this paper we propose a left-handed one that is made of dielectric tubes arranged in a close-packed hexagonal lattice. Without metallic cores, this structure is low-loss and convenient to fabricate. Negative refraction and its resulting focusing are investigated by dispersion characteristic analysis and numerical simulation of the field pattern. With proper modification at the interface, the image is improved. With better isotropy than that with noncircular rods, planoconcave lenses made by dielectric tubes focus a Gaussian beam exactly at R//n - 1/.

Crystal growth and spectroscopic characterization of Yb-doped and Yb, Na-codoped CaF2 laser crystals by TGT

High-quality 2at%-doped Yb:CaF2 and Yb,Na:CaF2 single crystals with diameter of 76mm were grown by the temperature gradient technique. For the first time, distribution coefficients (KO) of Yb in the two crystals were determined to be 1.07 and 0.91, respectively, by measuring the Yb concentrations at the growth starting position in the as-grown boules. Absorption and emission spectra of the two different crystals were measured at room temperature. Experimental results show that Na+ ions codoping with Yb3+ as charge compensators make Yb3+ ions in CaF2 lattice to be a quasi-single-center system, and greatly suppress the deoxidization of Yb3+ to Yb2+ (c) 2005 Elsevier B.V. All rights reserved.

Codoping Na+ to modulate the spectroscopy and photoluminescence properties of Yb3+ in CaF2 laser crystal

kinds of Yb3+- and Na+-codoped CaF2 laser crystal with different Na:Yb ratios of 0, 1.5, and 10 are grown by the temperature gradient technique. Room-temperature absorption, photoluminescence spectra, and fluorescence lifetimes belonging to the transitions between ground state F-2(7/2) and excited state F-2(5/2) of Yb3+ ions in the three crystals are measured to study the effect of Na+. Experimental results show that codoping Na+ ions in different Na:Yb ratios can modulate the spectroscopy and photoluminescence properties of Yb3+ ions in a CaF2 lattice in a large scope. (c) 2005 Optical Society of America

First-principles study of the electronic structures and absorption spectra for the PbMoO4 crystal with lead vacancy

The electronic structures and absorption spectra for the perfect PbMoO4 crystal and the crystal containing lead vacancy V-Pb(2-) with lattice structure optimized are calculated using density functional theory code CASTEP. The calculated absorption spectra of the PbMoO4 crystal containing V-Pb(2-) exhibit three absorption bands peaking at 2.0 eV (620 nm), 3.0 eV (413 run) and 3.3 eV (375 nm), which are in good agreement with experimental values. The theory predicts that the 390 nm, 430 nm and 580 run absorption bands are related to the existence of V-Pb(2-) in the PbMoO4 crystal.

Negative index photonic crystal lenses based on carbon nanotube arrays

We report a novel utilization of periodic arrays of carbon nanotubes in the realization of diffractive photonic crystal lenses. Carbon nanotube arrays with nanoscale dimensions (lattice constant 400 nm and tube radius 50 nm) displayed a negative refractive index in the optical regime where the wavelength is of the order of array spacing. A detailed computational analysis of band gaps and optical transmission through the nanotubes based planar, convex and concave shaped lenses was performed. Due to the negative-index these lenses behaved in an opposite fashion compared to their conventional counter parts. A plano-concave lens was established and numerically tested, displaying ultra-small focal length of 1.5 μm (∼2.3 λ) and a near diffraction-limited spot size of 400 nm (∼0.61 λ). © 2012 Elsevier B.V. All rights reserved.

Enhancement of room temperature sub-bandgap light emission from silicon photonic crystal nanocavity by Purcell effect

We report the enhancement of sub-bandgap photoluminescence from silicon via the Purcell effect. We couple the defect emission from silicon, which is believed to be due to hydrogen incorporation into the lattice, to a photonic crystal (PhC) nanocavity. We observe an up to 300-fold enhancement of the emission at room temperature at 1550 nm, as compared to an unpatterned sample, which is then comparable to the silicon band-edge emission. We discuss the possibility of enhancing this emission even further by introducing additional defects by ion implantation, or by treating the silicon PhC nanocavity with hydrogen plasma. © 2011 Elsevier B.V.

Proposal of an Ultracompact Triplexer Using Photonic Crystal Waveguide with an Air Holes Array

We propose an ultracompact triplexer based on a shift of the cutoff frequency of the fundamental mode in a planar photonic crystal waveguide (PCW) with a triangular lattice of air holes. The shift is realized by modifying the radii of the border holes adjacent to the PCW core. Some defect holes are introduced to control the beam propagation. The numerical results obtained by the finite-difference time-domain method show that the presented triplexer can separate three specific wavelengths, i.e. 1310, 1490 and 1550 nm with the extinction ratios higher than - 18 dB. The designed device with a size as compact as 12 mu m x 6.5 mu m is feasible for the practical application, and can be utilized in the system of fiber to the home.

High efficiency operation of butt joint line-defect-waveguide microlaser in two-dimensional photonic crystal slab

Butt joint line-defect-waveguide microlasers are demonstrated on photonic crystal slabs with airholes in a triangular lattice. Such microlaser is designed to increase the output power from the waveguide edge directly. The output power is remarkably enhanced to 214 times higher by introducing chirped structure in the output waveguide. The lasing mode operates in the linear dispersion region of the output waveguide so that the absorption loss due to the band-edge effect is reduced. The laser resonance is illustrated theoretically using the finite difference time domain method. A practical high power efficiency of 20% is obtained in this microlaser. (C) 2008 American Institute of Physics.

A ministop band in a single-defect photonic crystal waveguide based on silicon on insulator

This paper reports that a two-dimensional single-defect photonic crystal waveguide in the F-K direction with triangular lattice on a silicon-on-insulator substrate is fabricated by the combination of electron beam lithography and inductively coupled plasma etching. A ministop band (MSB) is observed by the measurement of transmission characteristics. It results from the coupling between the two modes with the same symmetry, which is analysed from the stimulated band diagram by the effective index and the two-dimensional plane wave expansion methods. The parameter working on the MSB is the ratio of the radius of air holes to the lattice constant, r/a. It is obtained that the critical r/a value determining the occurrence or disappearance of MSB is 0.36. When r/a is larger than or equal to 0.36, the MSB occurs. However, when r/a is smaller than 0.36, the MSB disappears.

Investigation of native defects and property of bulk ZnO single crystal grown by a closed chemical vapor transport method

Hall effect, Raman scattering, photoluminescence spectroscopy (PL), optical absorption (OA), mass spectroscopy, and X-ray diffraction have been used to study bulk ZnO single crystal grown by a closed chemical vapor transport method. The results indicate that shallow donor impurities (Ga and Al) are the dominant native defects responsible for n-type conduction of the ZnO single crystal. PL and OA results suggest that the as-grown and annealed ZnO samples with poor lattice perfection exhibit strong deep level green photoluminescence and weak ultraviolet luminescence. The deep level defect in as-grown ZnO is identified to be oxygen vacancy. After high-temperature annealing, the deep level photoluminescence is suppressed in ZnO crystal with good lattice perfection. In contrast, the photoluminescence is nearly unchanged or even enhanced in ZnO crystal with grain boundary or mosaic structure. This result indicates that a trapping effect of the defect exists at the grain boundary in ZnO single crystal. (C) 2007 Elsevier B.V. All rights reserved.

Slow wave effect of 2-D photonic crystal coupled cavity array

We designed a two-dimensional coupled photonic crystal resonator array with hexagonal lattice. The calculation by plane-wave-expansion method shows that the dispersion curve of coupled cavity modes in the bandgap are much flattened in all directions in the reciprocal space. We simulated the transmission spectra of transverse electric (TE) wave along the Gamma K direction. Compared with the PC single cavity structure, the transmission ratio of the coupled cavity array increases more than three orders of magnitude, while the group velocity decreases to below 1/10, reaching 0.007c. The slow wave effect has potential application in the field of miniaturized tunable optical delay components and low-threshold photonic crystal lasers.

High Polarization Single Mode Photonic Crystal Microlaser

Generally, dipole mode is a doubly degenerate mode. Theoretical calculations have indicated that the single dipole mode of two-dimensional photonic crystal single point defect cavity shows high polarization property. We present a structure with elongated lattice, which only supports a single y-dipole mode. With this structure we can eliminate the degeneracy, control the lasing action of the cavity and demonstrate the high polarization property of the single dipole mode. In our experiment, the polarization extinction ratio of the y-dipole mode is as high as 51 1.

Design of high polarization and single-mode photonic crystal laser

The dipole mode in triangular photonic crystal single defect cavity is degenerate. By deforming the lattice in photonic crystal we can obtain non-degenerate dipole modes. Lattice deforming in the whole photonic crystal destroys the characteristic of symmetry, so the distribution of the electromagnetic field is affected and the polarization of the electromagnetic field is also changed. Lattice deforming divides the degenerate dipole mode into the x-dipole mode and the y-dipole mode. It is found that the non-degenerate modes have better properties of polarization. So the high polarization and single dipole mode photonic crystal laser can be achieved by deforming the lattice of photonic crystal. In this paper, we simulated the cavity in photonic crystal slab and mainly calculated the quality factor of x-dipole mode under different deforming conditions and with different filling factors. The properties of polarization of x-dipole and y-dipole modes are also calculated. It is found that the ratio of intensities of E-x to E-y in x-dipole mode and that of E-y to E-x in y-dipole mode are 44 and 27, respectively.