Structural and spectral studies of novel Co(III) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde

Seven bis(ligand) Co(III) complexes {[CoL21] NO3 · H2 O (1), [CoL21] Cl · 2 H2 O (2),[CoL21] ClO4 (3), [CoL22] NO3 (4), [CoL22] Cl · 2 H2 O (5), [CoL23] Br · 2 H2 O (6), [CoL23] ClO4 · H2 O (7)} of three thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenylethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde-N(4)-(methyl),N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. All complexes are assigned octahedral geometries on the basis of spectral studies. The ligands deprotonate and coordinate by means of pyridine nitrogen, azomethine nitrogen, and thiolate sulfur atoms. The single crystal X-ray structures of HL3 and two nitrate compounds are discussed. The structural studies corroborate the spectral characterization.

Optimization of Preparation Techniques and Dielectric Study of Polyanilines in the Microwave & High Frequency Field

The thesis deals with the preparation and dielectric characterization of Poly aniline and its analogues in ISM band frequency of 2-4 GHz that includes part of the microwave region (300 MHz to 300 GHz) of the electromagnetic spectrum and an initial dielectric study in the high frequency [O.05MHz-13 MHz]. PolyaniIine has been synthesized by an in situ doping reaction under different temperature and in the presence of inorganic dopants such as HCl H2S04, HN03, HCl04 and organic dopants such as camphorsulphonic acid [CSA], toluenesulphonic acid {TSA) and naphthalenesulphonic acid [NSA]. The variation in dielectric properties with change in reaction temperature, dopants and frequency has been studied. The effect of codopants and microemulsions on the dielectric properties has also been studied in the ISM band. The ISM band of frequencies (2-4 GHz) is of great utility in Industrial, Scientific and Medical (ISM) applications. Microwave heating is a very efficient method of heating dielectric materials and is extensively used in industrial as well as household heating applications.

Acid base characteristics of binary oxides of Zr with Ce and La

The surface acidity and basicity of binary oxides of Zr with Ce and La are determined using a series of Hammet indicators and Ho,,max values are reported. The generation of new acid sites habe been ascribed to the charge imbalance of M1-O-M2 bonds, where M1 and M2 are metal atoms. Both Bronsted and Lewis acid sites contribute to the acidity of the oxides

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection is detected using a position sensitive detector and its output is fed to a lock-in-amplifIer from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

Evaluation of electrical conductivity and thermal diffusivity of vanadyl naphthalocyanine

The electrical conductivity and thermal diffusivity of pristine and iodine doped vanadyl naphthalocyanine (VONc) were studied. In the pristine sample, the temperature dependence was very weak below 300 K. The increase in conductivity at higher temperature must be due to an enhancement in carrier density with increase in thermal energy. The electrical conductivity of VONc increased when doped with iodine. The behavior of VONcI indicated that considerable changes have occurred in the electronic environment of the molecule as a result of doping. Iodine doping enhanced the thermal diffusivity of VONc. The increase in thermal diffusivity of the iodine doped sample may be due to the disorder of iodine atoms occupying the channels in one dimensional lattices.

Twin peak distribution of electron emission profile and impact ionization of ambient molecules during laser ablation of silver target

Laser-induced plasma generated from a silver target under partial vacuum conditions using the fundamental output of nanosecond duration from a pulsed Nd:yttrium aluminum garnet laser is studied using a Langmuir probe. The time of flight measurements show a clear twin peak distribution in the temporal profile of electron emission. The first peak has almost the same duration as the laser pulse while the second lasts for several microseconds. The prompt electrons are energetic enough ('60 eV) to ionize the ambient gas molecules or atoms. The use of prompt electron pulses as sources for electron impact excitation is demonstrated by taking nitrogen, carbon dioxide, and argon as ambient gases.

Time evolution of Nd:YAG laser-induced plasma from GdBa2Cu3O7 high-Tc superconductor

In order to characterise the laser ablation process from high-Tc superconductors, the time evolution of plasma produced by a Q-switching Nd:YAG laser from a GdBa2Cu3O7 superconducting sample has been studied using spectroscopic and ion-probe techniques. It has been observed that there is a fairly large delay for the onset of the emission from oxide species in comparison with those from atoms and ions of the constituent elements present in the plasma. Faster decay occurs for emission from oxides and ions compared with that from neutral atoms. These observations support the view that oxides are not directly produced from the target, but are formed by the recombination process while the plasma cools down. Plasma parameters such as temperature and velocity are also evaluated.

Compact dual band slot loaded circular microstrip antenna with a superstrate

Design of a compact dual frequency microstrip antenna is presented. The structure consists of a slotted circular patch with a dielectric superstrate. The superstrate,not only acts as a radome, but improves the bandwidth and lowers the resonant frequency also. The proposed design provides an overall size reduction of about 60% compared to an unslotted patch along with good efficiency,gain and bandwidth. The polarization planes at the two resonances are orthogonal and can be simultaneously excited using a coaxial feed. Parametric study of this configuration showed that the frequency ratio of the two resonances can be varied from 1.17 to 1.7 enabling its applications in the major wireless communication bands like AWS, DECT,PHS,Wi.Bro, ISM,and DMB. Design equations are also deduced for the proposed antenna and validated.

Studies on Non-Resonant Multiphoton Processes in Atomic Hydrogen

In the present thesis we have formulated the Dalgarno-Lewis procedure for two-and three-photon processes and an elegant alternate expressions are derived. Starting from a brief review on various multiphoton processes we have discussed the difficulties coming in the perturbative treatment of multiphoton processes. A small discussion on various available methods for studying multiphoton processes are presented in chapter 2. These theoretical treatments mainly concentrate on the evaluation of the higher order matrix elements coming in the perturbation theory. In chapter 3 we have described the use of Dalgarno-Lewis procedure and its implimentation on second order matrix elements. The analytical expressions for twophoton transition amplitude, two-photon ionization cross section, dipole dynamic polarizability and Kramers-Heiseberg are obtained in a unified manner. Fourth chapter is an extension of the implicit summation technique presented in chapter 3. We have clearly mentioned the advantage of our method, especially the analytical continuation of the relevant expressions suited for various values of radiation frequency which is also used for efficient numerical analysis. A possible extension of the work is to study various multiphoton processcs from the stark shifted first excited states of hydrogen atom. We can also extend this procedure for studying multiphoton processes in alkali atoms as well as Rydberg atoms. Also, instead of going for analytical expressions, one can try a complete numerical evaluation of the higher order matrix elements using this procedure.

Development of Free Space Method for Material Characterisation and GPR Study & A Case Study on Biological Samples

The thesis mainly focuses on material characterization in different environments: freely available samples taken in planar fonn, biological samples available in small quantities and buried objects.Free space method, finds many applications in the fields of industry, medicine and communication. As it is a non-contact method, it can be employed for monitoring the electrical properties of materials moving through a conveyor belt in real time. Also, measurement on such systems at high temperature is possible. NID theory can be applied to the characterization of thin films. Dielectric properties of thin films deposited on any dielectric substrate can be determined. ln chemical industry, the stages of a chemical reaction can be monitored online. Online monitoring will be more efficient as it saves time and avoids risk of sample collection.Dielectric contrast is one of the main factors, which decides the detectability of a system. lt could be noted that the two dielectric objects of same dielectric constant 3.2 (s, of plastic mine) placed in a medium of dielectric constant 2.56 (er of sand) could even be detected employing the time domain analysis of the reflected signal. This type of detection finds strategic importance as it provides solution to the problem of clearance of non-metallic mines. The demining of these mines using the conventional techniques had been proved futile. The studies on the detection of voids and leakage in pipes find many applications.The determined electrical properties of tissues can be used for numerical modeling of cells, microwave imaging, SAR test etc. All these techniques need the accurate determination of dielectric constant. ln the modem world, the use of cellular and other wireless communication systems is booming up. At the same time people are concemed about the hazardous effects of microwaves on living cells. The effect is usually studied on human phantom models. The construction of the models requires the knowledge of the dielectric parameters of the various body tissues. lt is in this context that the present study gains significance. The case study on biological samples shows that the properties of normal and infected body tissues are different. Even though the change in the dielectric properties of infected samples from that of normal one may not be a clear evidence of an ailment, it is an indication of some disorder.ln medical field, the free space method may be adapted for imaging the biological samples. This method can also be used in wireless technology. Evaluation of electrical properties and attenuation of obstacles in the path of RF waves can be done using free waves. An intelligent system for controlling the power output or frequency depending on the feed back values of the attenuation may be developed.The simulation employed in GPR can be extended for the exploration of the effects due to the factors such as the different proportion of water content in the soil, the level and roughness of the soil etc on the reflected signal. This may find applications in geological explorations. ln the detection of mines, a state-of-the art technique for scanning and imaging an active mine field can be developed using GPR. The probing antenna can be attached to a robotic arm capable of three degrees of rotation and the whole detecting system can be housed in a military vehicle. In industry, a system based on the GPR principle can be developed for monitoring liquid or gas through a pipe, as pipe with and without the sample gives different reflection responses. lt may also be implemented for the online monitoring of different stages of extraction and purification of crude petroleum in a plant.Since biological samples show fluctuation in the dielectric nature with time and other physiological conditions, more investigation in this direction should be done. The infected cells at various stages of advancement and the normal cells should be analysed. The results from these comparative studies can be utilized for the detection of the onset of such diseases. Studying the properties of infected tissues at different stages, the threshold of detectability of infected cells can be determined.

Density modes in spherical 4He shells

We compute the density-fluctuation spectrum of spherical 4HeN shells adsorbed on the outer surface of Cn fullerenes. The excitation spectrum is obtained within the random-phase approximation, with particle-hole elementary excitations and effective interaction extracted from a density-functional description of the shell structure. The presence of one or two solid helium layers adjacent to the adsorbing fullerene is phenomenologically accounted for. We illustrate our results for a selection of numbers of adsorbed atoms on C20, C60, and C120. The hydrodynamical model that has proven successful to describe helium excitations in the bulk and in restricted geometries permits to perform a rather exhaustive analysis of various fluid spherical systems, namely, spheres, cavities, free bubbles, and bound shells of variable size.

Formation and characterisation of indium selenide thin films by elemental evaporation

This thesis deals with preparing stoichiometric crystalline thin films of InSe and In2Se3 by elemental evapouration and their property investigation.In the present study three temperature( or Elemental evapouration) method is utilized for the deposition of crystalline thin films . The deposition mechanism using three temperature method deals’ with condensation of solids on heated surfaces when the critical supersaturation of the vapour phase exceeds a certain limit. The critical values of the incident flux are related to substrate temperature and the interfacial energies of the involved vapours. At a favorable presence of component atoms in the vapour phase these can react and condense onto a substrate even at a elevated temperature. In the studies conducted the most significant factor is the formation of single compositional film namely indium mono selenide in the In –se system of compounds .Further this work shows the feasibility of thin film photovoltaic junctions of the schottky barrier type

Transition metal complexes derived from ketone based N(4)-substituted thiosemicarbazones: Crystal structures and spectral studies

Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

Growth and characterisation of tin dichalcogenide crystals

During the past few decades, a wide spread interest in the structural, optical, electrical and other physical properties of the transition metal dichalcogenide layer compounds has evolved. The members of this family of compounds can be regarded as strongly bonded two dimensional chalcogen-metal~chalcogen layers which are loosely coupled to one another by the weak ven der Waal's forces. Because of this type of bonding, the crystals are easily cleavable along the basal plane and show highly anisotropic properties. This thesis contains the growth and the study of the physical properties of certain tin dichalcogenide crystals (SnS2 and SnSe2). Tin disulphide and tin diselenide crystallize in the hexagonal CdI2 type crystal structure. This structure consists of layers of tin atoms sandwiched between two layers of chalcogen atoms. A tin atom is surrounded by six chalcogen atoms octahedrally.In the layers the atoms are held together by covalent bonding and in between the layers there is van der Waal's bonding.

Growth and characterisation of tin dichalcogenide crystals

During the past few decades, a wide spread interest in the structural, optical, electrical and other physical properties of the transition metal dichalcogenide layer compounds has evolved. The members of this family of compounds can be regarded as stronglybonded two dimensional chalcogen-metal-chalcogen layers which are loosely coupled to one another by the weak van der Waal's forces. Because of this type of bonding, the crystals are easily cleavable along the basal plane and show highly anisotropic properties. This thesis contains the growth and the study of the physical properties of certain tin dichalcogenide crystals (SnS2 and Snsea). Tin disulphide and tin diselenide crystallize in the hexagonal CdI2 type crystalstructure. This structure consists of layers of tin atoms sandwiched between two layers of chalcogen atoms. Aitin atom is surrounded by six chalcogen atoms octahedrally. In the layers the atoms are held together by covalent bonding and in between the layers there is van der Waal's bonding.