Microwave spectroscopic and theoretical studies on the phenylacetylene center dot center dot center dot H(2)O complex: C-H center dot center dot center dot O and O-H center dot center dot center dot pi hydrogen bonds as equal partners

Rotational spectra of five isotopologues of the title complex, C(6)H(5)CCH center dot center dot center dot H(2)O, C(6)H(5)CCH center dot center dot center dot HOD, C(6)H(5)CCH center dot center dot center dot D(2)O, C(6)H(5)CCH center dot center dot center dot H(2)(18)O and C(6)H(5)CCD center dot center dot center dot H(2)O, were measured and analyzed. The parent isotopologue is an asymmetric top with kappa = -0.73. The complex is effectively planar (ab inertial plane) and both `a' and `b' dipole transitions have been observed but no c dipole transition could be seen. All the transitions of the parent complex are split into two resulting from an internal motion interchanging the two H atoms in H(2)O. This is confirmed by the absence of such doubling for the C(6)H(5)CCH center dot center dot center dot HOD complex and a significant reduction in the splitting for the D(2)O analog. The rotational spectra, unambiguously, reveal a structure in which H(2)O has both O-H center dot center dot center dot pi (pi cloud of acetylene moiety) and C-H center dot center dot center dot O (ortho C-H group of phenylacetylene) interactions. This is in agreement with the structure deduced by IR-UV double resonance studies (Singh et al., J. Phys. Chem. A, 2008, 112, 3360) and also with the global minimum predicted by advanced electronic structure theory calculations (Sedlack et al., J. Phys. Chem. A, 2009, 113, 6620). Atoms in Molecule (AIM) theoretical analysis of the complex reveals the presence of both O-H center dot center dot center dot pi and C-H center dot center dot center dot O hydrogen bonds. More interestingly, based on the electron densities at the bond critical points, this analysis suggests that both these interactions are equally strong. Moreover, the presence of both these interactions leads to significant deviation from linearity of both hydrogen bonds.

Preparation of a ZrO2–Al2O3 nanocomposite by high-pressure sintering of spray-pyrolyzed powders

ZrO2–Al2O3 powders were synthesized by spray pyrolysis. These powders were sintered at 1 GPa in the temperature range of 700–1100 °C. The microstructural evolution and densification are reported in this paper. The application of 1 Gpa pressure lowers the crystallization temperature from ∼850 to <700 °C. Similarly, the transformation temperature under 1 GPa pressure for γ → α–Al2O3 reduces from ∼1100 to 700–800 °C range, and that for t → m ZrO2 reduces from ∼1050 to 700–800 °C range. It was possible to obtain highly dense nanocrystalline ZrO2–Al2O3 composite at temperatures as low as 700 °C. The effect of high pressure on nucleation and transformation of phases is discussed.

Impact of satellite observed microwave SST on the simulation of tropical cyclones

The impact of realistic representation of sea surface temperature (SST) on the numerical simulation of track and intensity of tropical cyclones formed over the north Indian Ocean is studied using the Weather Research and Forecast (WRF) model. We have selected two intense tropical cyclones formed over the Bay of Bengal for studying the SST impact. Two different sets of SSTs were used in this study: one from TRMM Microwave Imager (TMI) satellite and other is the weekly averaged Reynold's SST analysis from National Center for Environmental Prediction (NCEP). WRF simulations were conducted using the Reynold's and TMI SST as model boundary condition for the two cyclone cases selected. The TMI SST which has a better temporal and spatial resolution showed sharper gradient when compared to the Reynold's SST. The use of TMI SST improved the WRF cyclone intensity prediction when compared to that using Reynold's SST for both the cases studied. The improvements in intensity were mainly due to the improved prediction of surface latent and sensible heat fluxes. The use of TMI SST in place of Reynold's SST improved cyclone track prediction for Orissa super cyclone but slightly degraded track prediction for cyclone Mala. The present modeling study supports the well established notion that the horizontal SST gradient is one of the major driving forces for the intensification and movement of tropical cyclones over the Indian Ocean.

Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

Microwave spectrum and structure of C(6)H(5)CCH center dot center dot center dot H(2)S complex

Rotational spectra of C(6)H(5)CCH center dot center dot center dot H(2)S, C(6)H(5)CCH center dot center dot center dot H(2)(34)S, C(6)H(5)CCH center dot center dot center dot HDS, C(6)H(5)CCH center dot center dot center dot D(2)S and C(6) H(5)CCD center dot center dot center dot H(2)S complexes have been observed using a pulsed nozzle Fourier transform microwave spectrometer. The observed spectrum is consistent with a structure in which hydrogen sulfide is located over the phenyl ring pi cloud and the distance between the centers of masses of the two monomers is 3.74 +/- 0.01 angstrom. In the complex, the H(2)S unit is shifted from the phenyl ring center towards the acetylene group. The vibrationally averaged structure has an effective Cs symmetry. Ab initio calculations were performed at MP2/aug-cc-pVDZ level of theory to locate the possible geometries of the complex. The calculations reveal the experimentally observed structure to be more stable than a coplanar arrangement of the monomers, which was observed for the C(6)H(5)CCH center dot center dot center dot H(2)O complex. Atoms in molecule theoretical analysis shows the presence of S-H center dot center dot center dot pi hydrogen bond. For the parent isotopologue, each transition frequency was found to split into two resulting from an interchange of the equivalent hydrogens of H(2)S unit in the complex. (C) 2011 Elsevier Inc. All rights reserved.

New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

A low cost approach for the fabrication of microwave phase shifter on laminates

This paper presents a simple and low cost fabrication approach using extended printed circuit board processing techniques for an electrostatically actuated phase shifter on a common microwave laminate. This approach uses 15 mu m thin copper foils for realizing the bridge structures as well as for a spacer. A polymeric thin film deposited by spin coating and patterned using lithographic process is used as a dielectric layer to improve the reliability of the device. The prototype of the phase shifter for X-band operation is fabricated and tested for electrical and electromechanical performance parameters. The realized devices have a figure of merit of 70 degrees/dB for a maximum applied bias potential of 85 V. Since these phase shifters can be conveniently fabricated directly on microwave substrates used for feed distribution networks of phased arrays, the overall addition in cost, dimensions and processing for including these phase shifters in these arrays is minimal.

Improved microwave dielectric properties of (Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics

Phase-singular solids of the composition, (Mg1−(x+y) Cax Lay)(Ti1−yAly)O3 (x = 0 to 0.88; y = 0.05 to 0.35) having the cubic perovskite-type structure were prepared by the substitution of La3+ and Al3+ in equivalent quantities which brought about complete miscibility between MgTiO3 and CaTiO3. These ceramics showed relative permittivities of 16.5 to 50 (at 6 GHz) with increasing Ca content, high Q values of 10 000 to 30 000 and retained near-zero temperature coefficients in permittivity at optimum y values. Their dielectric characteristics are better accountable in terms of the positional disorder rather than the tolerance factor of perovskite structure.

Microwave cavity resonators. Some perturbation effects and their applications

Lagrange's equation is utilized to show the analogy of a lossless microwave cavity resonator with the conventional LC network. A brief discussion on the resonant frequencies of a microwave cavity resonator and the two degenerate companion modes H01 and E11 appearing in a cavity is given. The first order perturbation theory of a small deformation of the wall of a cavity is discussed. The effects of perturbation, such as the change in the resonant frequency and the Q of a cavity, the change in the electromagnetic field configurations and hence mixing of modes are also discussed. An expression for the coupling coefficient between the two degenerate modes H01 and E11 is derived with the help of the field equations. Results indicate that in the absence of perturbation the above two degenerate modes can co-exist without losing their individual identities. Several applications of the perturbation theory, such as the measurement of the dielectric properties of matter, study of ferromagnetic resonance, etc., are described.

Nanocrystalline TiO(2) preparation by microwave route and nature of anatase-rutile phase transition in nano TiO(2)

Nanopowders of TiO(2) has been prepared using a microwave irradiation-assisted route, starting from a metalorganic precursor, bis(ethyl-3-oxo-butanoato)oxotitanium (IV), [TiO(etob)(2)](2). Polyvinylpyrrolidone (PVP) was used as a capping agent. The as-prepared amorphous powders crystallize into anatase phase, when calcined. At higher calcination temperature, the rutile phase is observed to form in increasing quantities as the calcination temperature is raised. The structural and physicochemical properties were measured using XRD, FT-IR, SEM, TEM and thermal analyses. The mechanisms of formation of nano-TiO(2) from the metal-organic precursor and the irreversible phase transformation of nano TiO(2) from anatase to rutile structure at higher temperatures have been discussed. It is suggested that a unique step of initiation of transformation takes place in Ti(1/2)O layers in anatase which propagates. This mechanism rationalizes several key observations associated with the anatase rutile transformation.

Spark plasma sintering of novel ZrB2-SiC-TiSi2 composites with better mechanical properties

We report here the development of ultrafine grained ZrB2-SiC composites using TiSi2 as the sintering aid and spark plasma sintering (SPS) as the processing technique. It was observed that the presence of TiSi2 improved the sinterability of the composites, such that near theoretical densification (99.9%) could be achieved for ZrB2-18 wt.% SiC-5 wt.% TiSi2 composites after SPS at 1600 degrees C for 10 min at 50 MPa. Use of innovative multi stage sintering (MSS) route, which involved holding the samples at lower (intermediate) temperatures for some time before holding at the final temperature, while keeping the net holding time to 10 min, allowed attainment of full densification of ZrB2-18 wt.% SiC-2.5 wt.% TiSi2 at a still lower final temperature of 1500 degrees C at 30 MPa. TEM observations, which revealed the presence of anisotropic ZrB2 grains with faceted grain boundaries and TiSi2 at the intergranular regions, suggested the occurrence of liquid phase sintering in the presence of TiSi2. No additional phase was detected in XRD as well as TEM, which confirmed the absence of any sintering reaction. The as developed composites possessed an excellent combination of Vickers hardness and indentation toughness, both of which increased with increase in TiSi2 content, such that the ZrBi2-18 wt.% SiC-5 wt.% TiSi2 (SPS processed at 1600 degrees C) possessed hardness of similar to 20 GPa and indentation toughness of similar to 5 MPa m(1/2). The use of MSS SPS at 1500 degrees C for ZrBi2-18 wt.% SiC-2.5 wt.% TiSi2 composite resulted in improvement in hardness of up to similar to 27 GPa and attainment of high flexural strength of similar to 455 MPa. (C) 2011 Elsevier B.V. All rights reserved.

Towards a broadband chirped pulse Fourier transform microwave spectrometer

This article gives a brief review of microwave spectroscopy and the experimental techniques used for obtaining microwave spectrum of molecules and complexes since 1950s. It presents a brief summary of the pulsed nozzle Fourier transform microwave (PNFTMW) spectrometer, fabricated in our laboratory, and discusses some of the important results obtained using the spectrometer. The most significant among the results from this spectrometer is the direct structural determination of weakly bound complexes involving H2O/H2S. These have challenged the conventional wisdom on hydrogen bonding leading us to propose a modern definition for the same through IUPAC. The limitations of the PNFTMW spectrometer and the need for the new chirped pulse Fourier transform microwave spectrometer are discussed as well. Moreover, preliminary results from our laboratory on generating a 1 A mu s chirped pulse of 1 GHz bandwidth are given.