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.

Plasmonic band gaps and waveguide effects in carbon nanotube arrays based metamaterials.

Highly dense periodic arrays of multiwalled carbon nanotubes behave like low-density plasma of very heavy charged particles, acting as metamaterials. These arrays with nanoscale lattice constants can be designed to display extended plasmonic band gaps within the optical regime, encompassing the crucial optical windows (850 and 1550 nm) simultaneously. We demonstrate an interesting metamaterial waveguide effect displayed by these nanotube arrays containing line defects. The nanotube arrays with lattice constants of 400 nm and radius of 50 nm were studied. Reflection experiments conducted on the nanoscale structures were in agreement with numerical calculations.

Fem modeling of periodic arrays of multi-walled carbon nanotubes

Multiwalled carbon nanotubes display dielectric properties similar to those of graphite, which can be calculated using the well known Drude-Lorentz model. However, most computational softwares lack the capacity to directly incorporate this model into the simulations. We present the finite element modeling of optical propagation through periodic arrays of multiwalled carbon nanotubes. The dielectric function of nanotubes was incorporated into the model by using polynomial curve fitting technique. The computational analysis revealed interesting metamaterial filtering effects displayed by the highly dense square lattice arrays of carbon nanotubes, having lattice constants of the order few hundred nanometers. The curve fitting results for the dielectric function can also be used for simulating other interesting optical applications based on nanotube arrays.

Plasmonic band gaps and waveguide effects in carbon nanotube arrays based metamaterials

Highly dense periodic arrays of multiwalled carbon nanotubes behave like low-density plasma of very heavy charged particles, acting as metamaterials. These arrays with nanoscale lattice constants can be designed to display extended plasmonic band gaps within the optical regime, encompassing the crucial optical windows (850 and 1550 nm) simultaneously. We demonstrate an interesting metamaterial waveguide effect displayed by these nanotube arrays containing line defects. The nanotube arrays with lattice constants of 400 nm and radius of 50 nm were studied. Reflection experiments conducted on the nanoscale structures were in agreement with numerical calculations.

Microstructure and strain analysis of GaN epitaxial films using in-plane grazing incidence x-ray diffraction

This paper investigates the major structural parameters, such as crystal quality and strain state of (001)-oriented GaN thin films grown on sapphire substrates by metalorganic chemical vapour deposition, using an in-plane grazing incidence x-ray diffraction technique. The results are analysed and compared with a complementary out-of-plane x-ray diffraction technique. The twist of the GaN mosaic structure is determined through the direct grazing incidence measurement of (100) reflection which agrees well with the result obtained by extrapolation method. The method for directly determining the in-plane lattice parameters of the GaN layers is also presented. Combined with the biaxial strain model, it derives the lattice parameters corresponding to fully relaxed GaN films. The GaN epilayers show an increasing residual compressive stress with increasing layer thickness when the two dimensional growth stage is established, reaching to a maximum level of -0.89 GPa.

Elasticity, band structure, and piezoelectricity of BexZn1-xO alloys

Lattice constants, elasticity, band structure and piezoelectricity of hexagonal wideband gap BexZn1-xO ternary alloys are calculatedusing firstprinciples methods. The alloys' lattice constants obey Vegard's law well. As Be concentration increases, the bulk modulus and Young's modulus of the alloys increase, whereas the piezoelectricity decreases. We predict that BexZn1-xO/GaN/substrate (x = 0.022) multilayer structure can be suitable for high-frequency surface acoustic wave device applications. Our calculated results are in good agreement with experimental data and other theoretical calculations. (c) 2008 Elsevier B.V. All rights reserved.

Effect of indium-doped interlayer on the strain relief in GaN films grown on Si(111)

Crack-free GaN films have been achieved by inserting an Indoped low-temperature (LT) AlGaN interlayer grown on silicon by metalorganic chemical vapor deposition. The relationship between lattice constants c and a obtained by X-ray diffraction analysis shows that indium doping interlayer can reduce the stress in GaN layers. The stress in GaN decreases with increasing trimethylindium (TMIn) during interlayer growth. Moreover, for a smaller TMIn flow, the stress in GaN decreases dramatically when In acts as a surfactant to improve the crystallinity of the AlGaN interlayer, and for a larger TMIn flow, the stress will increase again. The decreased stress leads to smoother surfaces and fewer cracks for GaN layers by using an In-doped interlayer than by using an undoped interlayer. In doping has been found to enhance the lateral growth and reduce the growth rate of the c face. It can explain the strain relief and cracks reduction in GaN films. (C) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of tensile stress in GaN grown on Si(111) by inserting a low-temperature AlN interlayer

This study describes the growth of a low-temperature AlN interlayer for crack-free GaN growth on Si(111). It is demonstrated that, in addition to the lower growth temperature, growth of the AlN interlayer under Al-rich conditions is a critical factor for crack-free GaN growth on Si(111) substrates. The effect of the AlN interlayer thickness and NH3/TMA1 ratios on the lattice constants of subsequently grown high temperature GaN was investigated by X-ray triple crystal diffraction. The results show that the elimination of micro-cracks is related to the reduction of the tensile stress in the GaN epitaxial layers. This was also coincident with a greater number of pits formed in the AlN interlayer grown under Al rich conditions. It is proposed that these pits act as centers for the generation of misfit dislocations, which in turn leads to the reduction of tensile stress. (C) 2004 Elsevier B.V. All rights reserved.

Photonic crystal vertical-cavity surface-emitting laser based on GaAs material

A photonic crystal vertical-cavity-surface-emitting laser ( PC-VCSEL) with a wavelength of about 850 nm was realized. The direct-current electrically-driven PC-VCSELs with a minimum threshold current of 2 mA and a maximum threshold current of 13.5 mA were obtained. We fabricated a series of PC-VCSEL chips whose lattice constants are in the range from 0.5 to 3 mu m with different filling factors, and found that the laser characterization depends on the lattice constant, the filling factor, the size of cavity, etc.

Structural characterization of AlGaN/GaN superlattices by x-ray diffraction and Rutherford backscattering

We report on structural characterization of AlGaN/GaN superlattices grown on sapphire. The superlattice formation is evidenced by high-resolution x-ray diffraction and transmission electron microscopy. The high resolution x-ray diffraction spectra exhibit a pattern of satellite peaks. The in-plane lattice constants of the superlattices indicate the coherent growth of the AlGaN layer onto GaN. The average At composition in the superlattices is determined to be 0.08 by Rutherford backscattering spectroscopy. The average parallel and perpendicular elastic strains for the SLs are determined to be (e(parallel to)) = +0.25% and (e(perpendicular to)) = -0.17%. (c) 2006 Elsevier Ltd. All rights reserved.

Anomalous strains in the cubic-phase GaN films grown on GaAs (001) by metalorganic chemical vapor deposition

Strains in cubic GaN films grown on GaAs (001) were measured by a triple-axis x-ray diffraction method. Residual strains in the as-grown epitaxial films were in compression, contrary to the predicted tensile strains caused by large lattice mismatch between epilayers and GaAs substrates (20%). It was also found that the relief of strains in the GaN films has a complicated dependence on the growth conditions. We interpreted this as the interaction between the lattice mismatch and thermal mismatch stresses. The fully relaxed lattice constants of cubic GaN are determined to be 4.5038 +/- 0.0009 Angstrom, which is in excellent agreement with the theoretical prediction of 4.503 Angstrom. (C) 2000 American Institute of Physics. [S0021-8979(00)07918-4].

Crystallographic and magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.

Hydrogenation and anisotropic expansions in R3Fe29-xTx (R = Y, Ce, Nd, Sm, Gd, Tb and Dy; T = V and Cr)

A systematic study of the phase formation, structure and magnetic properties of the R3Fe29-xTx compounds (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) has been performed upon hydrogenation. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions mainly along the a- and b-axis rather than along the c-axis are observed for all of the compounds upon hydrogenation. Hydrogenation leads to an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. First order magnetization processes (FOMP) occur in the external magnetic fields for Nd3Fe24.5Cr4.5H5.0, Tb3Fe27.0Cr2.0H2.8, and Gd3Fe28.0Cr1.0H4.2 compounds.

Structural and magnetic properties of hydrides R3Fe29-xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R3Fe29 - xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants a, b, and c and the unit cell volume of R3Fe29 - xVxHy decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce3Fe27.5V1.5H6.5, like Ce3Fe27.5V1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce3Fe27.5V1.5 and Gd3Fe28.4V0.6 show the larger storage of hydrogen with y = 6.5 and 6.9 in these hydrides. (C) 1998 Elsevier Science B.V. All rights reserved.

Crystallographic and magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic study of the structural and intrinsic magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Hydrogenation lends to a relative volume expansion of the unit cell and a decrease in x-ray density for each compound. Anisotropic expansions mainly along the n- and b-axes rather than along the c-axis for all of the compounds upon hydrogenation are observed. The lattice constants and the unit-cell volume of R3Fe29-xCrx and R3Fe29-xCrxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. After hydrogenation a decrease of 0.34 mu(B)/Fe in the average Fe atomic magnetic moment and a slight increase in the anisotropy field for Y3Fe27.2Cr1.8 are achieved at 4.2 K. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and TD3Fe27.0Cr2.0H2.8, and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2. The abnormal crystallographic and magnetic properties of Ce3Fe25.0Cr4.0 and Ce3Fe25.0Cr4.0H5.4 suggest that the Ce ion non-triply ionized.