Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

Investigation of structural, optical and electrical properties and valence band splitting in cu-ln-se compounds

Investigations on thin films that started decades back due to scientific curiosity in the properties of a two-dimensional solid, has developed into a leading research field in recent years due to the ever expanding applications of the thin films in the fann of a variety of active and passive microminiaturized components and devices, solar cells, radiation sowces and detectors, magnetic memory devices, interference filters, refection and antireflection coatings etc. [1]. The recent environment and energy resource concerns have aroused an enonnous interest in the study of materials in thin film form suitable for renewable energy sources such as photovoltaic devices. Recognition of the immense potential applications of the chalcopyrites that can fonn homojunctions or heterojunctions for solar cell fabrication has attracted many researchers to extensive and intense research on them. In this thesis, we have started with studies performed on CuInSe, thin films, a technologically well recognized compound belonging to the l•ill-VI family of semiconductors and have riveted on investigations on the preparation and characterization of compoWlds Culn3Se5. Culn5Seg and CuIn7Se12, an interesting group of compounds related to CuInSe2 called Ordered Vacancy Compounds, having promising applications in photovoltaic devices. A pioneering work attempted on preparing and characterizing the compound Culn7Sel2 is detailed in the chapters on OVC's. Investigation on valence band splitting in avc's have also been attempted for the first time and included as the last chapter in the thesis. Some of the salient features of the chalcopyrite c.ompounds are given in the next section .of this introductory chapter.

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

“Investigations on Vibrational Overtones in the NIR region and Laser Induced Fluorescence in some selected compounds”

The central theme of this research concerns the study of vibrationally excited molecules. We have used the local mode description of such vibrational states, and this -model has now gained general acceptance. A central feature of the model is the Wloealizafion of vibrational energy. A study of these high—energy localized states provides example, becauseof this localization, overtone spectra, which measure the absorption of T vibrational energy, are extremely sensitive to the properties of X-H bonds. We also use -overtone spectra to study the conformation of molecules, i.e., the relative internal orientation of their bonds. The thesis comprises six chapters

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.

Using Neural Network Classifier Support Vector Machine Regression for the prediction of Melting Point of Drug – like compounds

In our study we use a kernel based classification technique, Support Vector Machine Regression for predicting the Melting Point of Drug – like compounds in terms of Topological Descriptors, Topological Charge Indices, Connectivity Indices and 2D Auto Correlations. The Machine Learning model was designed, trained and tested using a dataset of 100 compounds and it was found that an SVMReg model with RBF Kernel could predict the Melting Point with a mean absolute error 15.5854 and Root Mean Squared Error 19.7576

On the Growth Mechanism of Nickel and Cobalt Nanowires and Comparison of Their Magnetic Properties

Magnetic nanowires (NWs) are ideal materials for the fabrication of various multifunctional nanostructures which can be manipulated by an external magnetic fi eld. Highly crystalline and textured nanowires of nickel (Ni NWs) and cobalt (Co NWs) with high aspect ratio (~330) and high coercivity have been synthesized by electrodeposition using nickel sulphate hexahydrate (NiSO4·6H2O) and cobalt sulphate heptahydrate (CoSO4·7H2O) respectively on nanoporous alumina membranes. They exhibit a preferential growth along〈110〉. A general mobility assisted growth mechanism for the formation of Ni and Co NWs is proposed. The role of the hydration layer on the resulting one-dimensional geometry in the case of potentiostatic electrodeposition is verified. A very high interwire interaction resulting from magnetostatic dipolar interactions between the nanowires is observed. An unusual low-temperature magnetisation switching for fi eld parallel to the wire axis is evident from the peculiar high fi eld M(T) curve

Synthesis of High Coercivity Core–Shell Nanorods Based on Nickel and Cobalt and Their Magnetic Properties

Hybrid magnetic nanostructures with high coercivity have immense application potential in various fields. Nickel (Ni) electrodeposited inside Cobalt (Co) nanotubes (a new system named Ni @ Co nanorods) were fabricated using a two-step potentiostatic electrodeposition method. Ni @ Co nanorods were crystalline, and they have an average diameter of 150 nm and length of *15 lm. The X-ray diffraction studies revealed the existence of two separate phases corresponding to Ni and Co. Ni @ Co nanorods exhibited a very high longitudinal coercivity. The general mobility-assisted growth mechanism proposed for the growth of one-dimensional nanostructures inside nano porous alumina during potentiostatic electrodeposition is found to be valid in this case too

Template-Assisted Synthesis and Characterization of Passivated Nickel Nanoparticles

Potential applications of nickel nanoparticles demand the synthesis of self-protected nickel nanoparticles by different synthesis techniques. A novel and simple technique for the synthesis of self-protected nickel nanoparticles is realized by the inter-matrix synthesis of nickel nanoparticles by cation exchange reduction in two types of resins. Two different polymer templates namely strongly acidic cation exchange resins and weakly acidic cation exchange resins provided with cation exchange sites which can anchor metal cations by the ion exchange process are used. The nickel ions which are held at the cation exchange sites by ion fixation can be subsequently reduced to metal nanoparticles by using sodium borohydride as the reducing agent. The composites are cycled repeating the loading reduction cycle involved in the synthesis procedure. X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron microscopy, Energy Dispersive Spectrum, and Inductively Coupled Plasma Analysis are effectively utilized to investigate the different structural characteristics of the nanocomposites. The hysteresis loop parameters namely saturation magnetization and coercivity are measured using Vibrating Sample Magnetometer. The thermomagnetization study is also conducted to evaluate the Curie temperature values of the composites. The effect of cycling on the structural and magnetic characteristics of the two composites are dealt in detail. A comparison between the different characteristics of the two nanocomposites is also provided

Nonlinear and magneto-optical transmission studies on magnetic nanofluids of non-interacting metallic nickel nanoparticles

Oxide free stable metallic nanofluids have the potential for various applications such as in thermal management and inkjet printing apart from being a candidate system for fundamental studies. A stable suspension of nickel nanoparticles of ∼5 nm size has been realized by a modified two-step synthesis route. Structural characterization by x-ray diffraction and transmission electron microscopy shows that the nanoparticles are metallic and are phase pure. The nanoparticles exhibited superparamagnetic properties. The magneto-optical transmission properties of the nickel nanofluid (Ni-F) were investigated by linear optical dichroism measurements. The magnetic field dependent light transmission studies exhibited a polarization dependent optical absorption, known as optical dichroism, indicating that the nanoparticles suspended in the fluid are non-interacting and superparamagnetic in nature. The nonlinear optical limiting properties of Ni-F under high input optical fluence were then analyzed by an open aperture z-scan technique. The Ni-F exhibits a saturable absorption at moderate laser intensities while effective two-photon absorption is evident at higher intensities. The Ni-F appears to be a unique material for various optical devices such as field modulated gratings and optical switches which can be controlled by an external magnetic field

Effect of nickel nanofillers on the dielectric and magnetic properties of composites based on rubber in the X-band

Nickel–rubber nanocomposites were synthesized by incorporating ferromagnetic nickel nanoparticles in a natural rubber as well as neoprene rubber matrix. Complex dielectric permittivity and magnetic permeability of these composites were evaluated in the X-band microwave frequencies at room temperature using cavity perturbation technique. The dielectric loss in natural rubber is smaller compared to neoprene rubber. A steady increase in the dielectric permittivity is observed with increase in the content of nickel in both the composites. The magnetic permeability exhibits a steady decrease with increase in frequency and magnetic loss shows a relaxation at 8 GHz. The suitability of these composites as microwave absorbers is modeled based on the reflection loss which is dependant on the real and imaginary components of the complex dielectric permittivity and magnetic permeability.

Cure Characteristics and Mechanical Properties of Rubber Ferrite Composites Based on Nano-Nickel Ferrites

Ultra fine nickel ferrite have been synthesized by the sol-gel method. By heat treating different portions of the prepared powder separately at different temperatures, nano-sized particles of nickel ferrite with varying particle sizes were obtained. These powders were characterised by the X-ray diffraction and then incorporated in the nitrile rubber matrix according to a specific recipe for various loadings. The cure characteristics and the mechanical properties of these rubber ferrite composites (RFCs) were evaluated. The effect of loading and the grain size of the filler on the cure characteristics and tensile properties were also evaluated. It is found that the grain size and porosity of the filler plays a vital role in determining the mechanical properties of the RFCs

4,5-Dihydro-1,3-dioxepine als chirale Bausteine in der enantioselektiven organischen Synthese

Durch asymmetrische Doppelbindungsisomerisierung mittels Me-DuPHOS-modifizierter Dihalogen-Nickel-Komplexe als Katalysatorvorstufen lassen sich aus 2-Alkyl-4,7-dihydro-1,3-dioxepinen hochenantiomerenreine 2-Alkyl-4,5-dihydro-1,3-dioxepine erhalten. Ein Ziel dieser Arbeit war es, die bisher noch unbekannte Absolutkonfiguration dieses Verbindungstyps zu bestimmen und darüber hinaus ihre Einsatzfähigkeit in der enantioselektiven organischen Synthese zu untersuchen. Zu diesem Zweck wurden enantiomerenangereichertes 2-Isopropyl- und 2-tert-Butyl-4,5-dihydro-1,3-dioxepin mit m-Chlorperbenzoesäure epoxidiert. Dabei bildeten sich die entsprechenden 3-Chlorbenzoesäure-(2-alkyl-5-hydroxy-1,3-dioxepan-4yl)-ester in hohen Ausbeuten und Diastereoselektivitäten. Von den vier zu erwartenden Diastereomeren wurden jeweils nur zwei mit einer Selektivität von mehr als 95:5 gebildet. Im Fall des 3-Chlorbenzoesäure-(2-isopropyl-5-hydroxy-1,3-dioxepan-4yl)-esters konnte das Haupt-diastereomer kristallin erhalten werden. Durch röntgenspektroskopische Untersuchung war es möglich, die Relativ-Konfiguration dieser Verbindung zu bestimmen. Die Ester lassen sich unter Ringverengung in 2-Alkyl-1,3-dioxan-4-carbaldehyde umlagern. Ausgehend von diesen Carbaldehyden stehen zwei Synthesewege zur Verfügung, welche zu Verbindungen führen deren Absolutkonfiguration bereits bekannt ist. So erhält man durch Reduktion 2-Alkyl-1,3-dioxan-4-yl-methanole, welche sich in 1,2,4-Butantriol überführen lassen. Oxidation ergibt die 2-Alkyl-1,3-dioxan-4-carbonsäuren, aus denen 3-Hydroxytetrahydrofuran-2-on gewonnen werden kann. Messung des Drehwertes dieser beiden literaturbekannten Verbindungen liefert nicht nur Information über deren Enantiomerenreinheit sondern ebenfalls über die Konfiguration ihres Stereozentrums. In Kombination mit der Relativ-Konfiguration des Esters ist somit ein Rückschluss auf die Absolutkonfiguration der eingesetzten 4,5-Dihydro-1,3-dioxepine möglich. Die auf den beschriebenen Wegen gewonnenen Substanzen finden Anwendung in der stereoselektiven organischen Synthese. Löst man die Chlorbenzoesäureester in Dichlormethan und behandelt sie mit wässriger Salzsäure, so entstehen die bicyclischen 2-Alkyltetrahydrofuro[2,3-d][1,3]dioxole. Auch bei diesen Verbindungen konnten hohe Enantio- und Diastereoselektivitäten erzielt werden. Der intermolekular verlaufende Reaktionsmechanismus der Bicyclus-Bildung, welcher unter Abspaltung eines den Alkylrest tragenden Aldehyds und dessen Neuanlagerung unter Ausbildung eines Acetals verläuft, konnte in dieser Arbeit durch ein Kreuzungsexperiment bestätigt werden. Umacetalisierung der Bicyclen liefert 2-Methoxytetrahydrofuran-3-ol, aus dem durch Acetalspaltung Tetrahydrofuran-2,3-diol erhalten wird, das die Halbacetalform der entsprechenden Desoxytetrose darstellt, die auf diese Weise in einer de novo-Synthese hergestellt werden kann.

Prediction of some thermodynamic properties of selected compounds of element 104

A set of parametrized equations has been published by Bratsch and Lagowski for calculating thermodynamic properties of the lanthanides, actinides, element 104, and certainrelated elements. Since these equations were applied to element 104, new values for the first four ionization energies and radii of the ions of charge +1, +2, +3, and +4 have been calculated for this element. The parametrized equations are used here with these new values to calculate some thermodynamic properties of element 104.