Investigations on the Structural, Spectral and Magnetic Interactions of Transition Metal Complexes of Multidentate Ligands from Di-2-pyridyl ketone and N(4)-substituted Thiosemicarbazides

The present work deals with the investigations on sthe structural spectral and magnetic interactions of transition metal complexes of multidentate ligands from D1-2-pyridyl ketone and N(4)-Substituted thiosemicarbazides.Thiosemicarbazones are thiourea derivatives with the general formula R2N— C(S)—NH—N=CR2. In the solution state, the thiosemicarbazones exhibit the thionethiol tautomerism similar to the keto-enol tautomerism, and in solution state the thiol form predominates and a deprotonation at the thiolate group in alcoholic medium enhances the coordination abilities ofthe thiosemicarbazones.The magnetochemistry of metal complexes of di-2-pyridyl ketone is a current hot subject of research, which mainly owes to the excellent structural diversity of the complexes ranging from cubanes to clusters, with promising ferromagnetic outputs.Only few efforts were aimed at the magnetochemistry of metal complexes of thiosemicarbazones, and that too were concerned with the complexes of bisttltioscinicarbazones). However, as far as the monothiosemicarbazones are concerned, the magnetochemistry of transition metal complexes of di-2-pyridyl ketone thiosemicarbazones turned up quite unexplored. Consequently, an investigation into it appeared novel and promising to us and that prompted this study, which can be regarded as the initial step towards exploring the magnetochemistry of thiosemicarbazone complexes, especially of di-2-pyridyl ketone derivatives.We could successfully isolate single crystals suitable for X-ray diffraction for the first three ligands. To conclude, we have synthesized some new thiosemicarbazones and their transition metal complexes and studied their structural, spectral and magnetic attributes. Some ofthe complexes revealed interesting stereochemistries and possible bridging characteristics with spectroscopic evidences. Unfortunately, single crystal Xray diffraction studies could not be carried out for many of these interesting compounds due to the lack of availability of suitable quality single crystals. However, the magnetic studies provided support for the proposed stereochemistry giving evidences for their magnetically concentrated nature. The magnetic susceptibilities measured at six different temperatures in the 80-298 K range are fitted into different magnetic equations, which provided an idea about the magnetic behavior of the compounds under study. Some of the copper, oxovanadium, nickel and cobalt complexes are found to possess anomalous magnetic moments, i.e., they revealed no regular gradation with temperature. However, some other copper complexes are observed to be antiferromagnetic, due to super-exchange pathways. The manganese complexes and one of the cobalt complexes are also observed to be antiferromagnetic in nature. However, some nickel complexes have turned up to be ferromagnetic. Accordingly, the versatile stereoehemistry and magnetic behavior of the complexes studied, prompt us to conclude that the transition metal complexes of di-2-pyridyl ketone thiosemicarbazones are promising systems for potential magnetic applications.

Exchange-correlation effects on quantum wires with spin-orbit interactions under the influence of in-plane magnetic fields.

Within the noncollinear local spin-density approximation, we have studied the ground state structure of a parabolically confined quantum wire submitted to an in-plane magnetic field, including both Rashba and Dresselhaus spin-orbit interactions. We have explored a wide range of linear electronic densities in the weak (strong) coupling regimes that appear when the ratio of spin-orbit to confining energy is small (large). These results are used to obtain the conductance of the wire. In the strong coupling limit, the interplay between the applied magnetic field¿irrespective of the in-plane direction, the exchange-correlation energy, and the spin-orbit energy-produces anomalous plateaus in the conductance vs linear density plots that are otherwise absent, or washes out plateaus that appear when the exchange-correlation energy is not taken into account.

Power Profile of Effective Managers: An Exploration among the Branch Managers of a Commercial Bank in Kerala

Managers are central to any fuction in a complex and developed society. Their talents are reckoned to be cardinal in developed economies and a basic yearning of all developing economies.In order to survive and produce results in a turbulent and transient environment, the task is to understand the nature of factors contributing to managerial effectiveness. This study is an attempt towards this core issue of the present from a different perspective. This study tries to focus attention on a group of managers functioning in the field of banking, a core sector in the country's economy. The gamut of economic activities in Kerala being predominantly service-oriented, importance of commercial banking is almost indisputable. Though economists would argue that the disproportionate development of service sector is anomalous when viewed against the hazy scenarios in the primary and secondary sectors of the state’s economy, the extent and pace of growth in the banking sector has had its dole meted out by ambitious and productive managers fiinctioning in the field. Researcher’s attempt here is to thresh the grain and chaff among bank managers in terms of their effectiveness and to account for the variations in the light of their ability to affect the thoughts and actions of their subordinates. To put it succinctly, the attempt herein is to explain the effectiveness of bank managers in the light of their ‘Power Profile’ taken to be comprising Power Differentials, Power Bases, their Visibility and Credibility in the organisation and, the Power Styles typically used by them for influencing subordinates.

Shot noise anomalies in elastic nondegenerate diffusive conductors

We present a theoretical investigation of shot-noise properties in nondegenerate elastic diffusive conductors. Both Monte Carlo simulations and analytical approaches are used. Two interesting phenomena are found: (i) the display of enhanced shot noise for given energy dependences of the scattering time, and (ii) the recovery of full shot noise for asymptotic high applied bias. The first phenomenon is associated with the onset of negative differential conductivity in energy space that drives the system towards a dynamical electrical instability in excellent agreement with analytical predictions. The enhancement is found to be strongly amplified when the dimensionality in momentum space is lowered from three to two dimensions. The second phenomenon is due to the suppression of the effects of long-range Coulomb correlations that takes place when the transit time becomes the shortest time scale in the system, and is common to both elastic and inelastic nondegenerate diffusive conductors. These phenomena shed different light in the understanding of the anomalous behavior of shot noise in mesoscopic conductors, which is a signature of correlations among different current pulses.

Ferromagnetic instabilities in neutron matter at finite temperature with the Skyrme interaction

The properties of spin-polarized neutron matter are studied at both zero and finite temperature using Skyrme-type interactions. It is shown that the critical density at which ferromagnetism takes place decreases with temperature. This unexpected behavior is associated to an anomalous behavior of the entropy that becomes larger for the polarized phase than for the unpolarized one above a certain critical density. This fact is a consequence of the dependence of the entropy on the effective mass of the neutrons with different third spin component. A new constraint on the parameters of the effective Skyrme force is derived if this behavior is to be avoided.

Variation in radio refractivity index associated with formation of low - pressure systems

Numerous low - pressure systems form in the Arabian Sea and Bay of Bengal. These low-pressure systems are highly useful in bringing the rainfall over the Indian sub continent. The developments of these systems are accompanied by the reduction in air temperature and an increase in atmospheric humidity. The radio refractivity, which is a function of the atmospheric pressure, temperature and humidity, also changes following the development of these systems. Variation of radio refractive index and its vertical gradient are analysed for many low pressure systems formed over the Arabian Sea and Bay of Bengal. It is found that the atmosphere becomes super refractive associated with the formation of these systems, caused by the increase in humidity and decrease in temperature. The maximum gradient is observed near the surface layers, especially in the lowest 1 km. Super refraction leads to increased radar detection range and extension of radio horizon

Drastic variation in the surface boundary layer parameters over Cochin during the annular solar eclipse: Analysis using sonic anemometer data

Atmospheric surface boundary layer parameters vary anomalously in response to the occurrence of annular solar eclipse on 15th January 2010 over Cochin. It was the longest annular solar eclipse occurred over South India with high intensity. As it occurred during the noon hours, it is considered to be much more significant because of its effects in all the regions of atmosphere including ionosphere. Since the insolation is the main driving factor responsible for the anomalous changes occurred in the surface layer due to annular solar eclipse, occurred on 15th January 2010, that played very important role in understanding dynamics of the atmosphere during the eclipse period because of its coincidence with the noon time. The Sonic anemometer is able to give data of zonal, meridional and vertical wind as well as the air temperature at a temporal resolution of 1 s. Different surface boundary layer parameters and turbulent fluxes were computed by the application of eddy correlation technique using the high resolution station data. The surface boundary layer parameters that are computed using the sonic anemometer data during the period are momentum flux, sensible heat flux, turbulent kinetic energy, frictional velocity (u*), variance of temperature, variances of u, v and w wind. In order to compare the results, a control run has been done using the data of previous day as well as next day. It is noted that over the specified time period of annular solar eclipse, all the above stated surface boundary layer parameters vary anomalously when compared with the control run. From the observations we could note that momentum flux was 0.1 Nm 2 instead of the mean value 0.2 Nm-2 when there was eclipse. Sensible heat flux anomalously decreases to 50 Nm 2 instead of the mean value 200 Nm 2 at the time of solar eclipse. The turbulent kinetic energy decreases to 0.2 m2s 2 from the mean value 1 m2s 2. The frictional velocity value decreases to 0.05 ms 1 instead of the mean value 0.2 ms 1. The present study aimed at understanding the dynamics of surface layer in response to the annular solar eclipse over a tropical coastal station, occurred during the noon hours. Key words: annular solar eclipse, surface boundary layer, sonic anemometer

Formation of anoxia and denitrification in the bottom waters of a tropical estuary, southwest coast of India

Hydrographic characteristics of the southwest coast of India and its adjoining Cochin backwaters (CBW) were studied during the summer monsoon period. Anomalous formation of anoxia and denitrification were observed in the bottom layers of CBW, which 5 have not been previously reported elsewhere in any tropical estuarine systems. The prevalent upwelling in the Arabian Sea (AS) brought cool, high saline, oxygen deficient and nutrient-rich waters towards the coastal zone and bottom layers of CBW during the high tide. High freshwater discharge in the surface layers brought high amount of nutrients and makes the CBW system highly productive. Intrusion of AS waters seems 10 to be stronger towards the upstream end ( 15 km), than had been previously reported, as a consequence of the lowering of river discharges and deepening of channels in the estuary. Time series measurements in the lower reaches of CBW indicated a low mixing zone with increased stratification, 3 h after the high tide (highest high tide) and high variation in vertical mixing during the spring and neap phases. The upwelled waters 15 (O2 40 μM) intruded into the estuary was found to lose more oxygen during the neap phase (suboxic O2 4 μM) than spring phase (hypoxic O2 10 μM). Increased stratification coupled with low ventilation and presence of high organic matter have resulted in an anoxic condition (O2 = 0), 2–6 km away from barmouth of the estuary and leads to the formation of hydrogen sulphide. The reduction of nitrate and formation of nitrite 20 within the oxygen deficient waters indicated strong denitrification intensity in the estuary. The expansion of oxygen deficient zone, denitrification and formation of hydrogen sulphide may lead to a destruction of biodiversity and an increase of green house gas emissions from this region

Local Hadley circulation over the Asian monsoon region associated with the Tropospheric Biennial Oscillation

The Tropospheric Biennial Oscillation (TBO), a major interannual variation phenomenon in the Indo-Pacific region, is the result of strong ocean-atmosphere coupling over the Asian-Australian monsoon area. Along with other meteorological and oceanographic parameters, the tropical circulation also exhibits interannual oscillations. Even though the TBO is the result of strong air–sea interaction, the circulation cells during TBO years are, as yet, not well understood. In the present study, an attempt has been made to understand the interannual variability of the mean meridional circulation and local monsoon circulation over south Asia in connection with the TBO. The stream function computed from the zonal mean meridional wind component of NCEP=NCAR reanalysis data for the years 1950–2003 is used to represent the meanmeridional circulation. Mean meridional mass transport in the topics reverses from a weak monsoon to a strong monsoon in the presence of ENSO, but in normal TBO yearsmean transport remains weak across the Northern Hemisphere. The meridional temperature gradient, which drives the mean meridional circulation, also shows no reversal during the normal TBO cycle. The local Hadley circulation over the monsoon area follows the TBO cycle with anomalous ascent (descent) in strong (weak) monsoon years. During normal TBO years, the Equatorial region and Indian monsoon areas exhibit opposite local Hadley circulation anomalies

Synthesis and Photoluminescence Properties of Novel Red Phosphors for White Light Emitting Diode Applications

Several series of Eu3+ based red emitting phosphor materials were synthesized using solid state reaction route and their properties were characterized. The present studies primarily investigated the photoluminescence properties of Eu3+ in a family of closely related host structure with a general formula Ln3MO7. The results presented in the previous chapters throws light to a basic understanding of the structure, phase formation and the photoluminescence properties of these compounds and their co-relations. The variation in the Eu3+ luminescence properties with different M cations was studied in Gd3-xMO7 (M = Nb, Sb, Ta) system.More ordering in the host lattice and more uniform distribution of Eu3+ ions resulting in the increased emission properties were observed in tantalate system.Influence of various lanthanide ion (Lu, Y, Gd, La) substitutions on the Eu3+ photoluminescence properties in Ln3MO7 host structures was also studied. The difference in emission profiles with different Ln ions demonstrated the influence of long range ordering, coordination of cations and ligand polarizability in the emission probabilities, intensity and quantum efficiency of these phosphor materials. Better luminescence of almost equally competing intensities from all the 4f transitions of Eu3+ was noticed for La3TaO7 system. Photoluminescence properties were further improved in La3TaO7 : Eu3+ phosphors by the incorporation of Ba2+ ions in La3+ site. New red phosphor materials Gd2-xGaTaO7 : xEu3+ exhibiting intense red emissions under UV excitation were prepared. Optimum doping level of Eu3+ in these different host lattices were experimentally determined. Some of the prepared samples exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. In the present studies, Eu3+ acts as a structural probe determining the coordination and symmetry of the atoms in the host lattice. Results from the photoluminescence studies combined with the powder XRD and Raman spectroscopy investigations helped in the determination of the correct crystal structures and phase formation of the prepared compounds. Thus the controversy regarding the space groups of these compounds could be solved to a great extent. The variation in the space groups with different cation substitutions were discussed. There was only limited understanding regarding the various influential parameters of the photoluminescence properties of phosphor materials. From the given studies, the dependence of photoluminescence properties on the crystal structure and ordering of the host lattice, site symmetries, polarizability of the ions, distortions around the activator ion, uniformity in the activator distribution, concentration of the activator ion etc. were explained. Although the presented work does not directly evidence any application, the materials developed in the studies can be used for lighting applications together with other components for LED lighting. All the prepared samples were well excitable under near UV radiation. La3TaO7 : 0.15Eu3+ phosphor with high efficiency and intense orange red emissions can be used as a potential red component for the realization of white light with better color rendering properties. Gd2GaTaO7 : Eu3+, Bi2+ red phosphors give good color purity matching to NTSC standards of red. Some of these compounds exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. However thermal stability and electrical output using these compounds should be studied further before applications. Based on the studies in the closely related Ln3MO7 structures, some ideas on selecting better host lattice for improved luminescence properties could be drawn. Analyzing the CTB position and the number of emission splits, a general understanding on the doping sites can be obtained. These results could be helpful for phosphor designs in other host systems also, for enhanced emission intensity and efficiency.

A computer-algebraic approach to the study of the symmetry properties of molecules and clusters

This thesis work is dedicated to use the computer-algebraic approach for dealing with the group symmetries and studying the symmetry properties of molecules and clusters. The Maple package Bethe, created to extract and manipulate the group-theoretical data and to simplify some of the symmetry applications, is introduced. First of all the advantages of using Bethe to generate the group theoretical data are demonstrated. In the current version, the data of 72 frequently applied point groups can be used, together with the data for all of the corresponding double groups. The emphasize of this work is placed to the applications of this package in physics of molecules and clusters. Apart from the analysis of the spectral activity of molecules with point-group symmetry, it is demonstrated how Bethe can be used to understand the field splitting in crystals or to construct the corresponding wave functions. Several examples are worked out to display (some of) the present features of the Bethe program. While we cannot show all the details explicitly, these examples certainly demonstrate the great potential in applying computer algebraic techniques to study the symmetry properties of molecules and clusters. A special attention is placed in this thesis work on the flexibility of the Bethe package, which makes it possible to implement another applications of symmetry. This implementation is very reasonable, because some of the most complicated steps of the possible future applications are already realized within the Bethe. For instance, the vibrational coordinates in terms of the internal displacement vectors for the Wilson's method and the same coordinates in terms of cartesian displacement vectors as well as the Clebsch-Gordan coefficients for the Jahn-Teller problem are generated in the present version of the program. For the Jahn-Teller problem, moreover, use of the computer-algebraic tool seems to be even inevitable, because this problem demands an analytical access to the adiabatic potential and, therefore, can not be realized by the numerical algorithm. However, the ability of the Bethe package is not exhausted by applications, mentioned in this thesis work. There are various directions in which the Bethe program could be developed in the future. Apart from (i) studying of the magnetic properties of materials and (ii) optical transitions, interest can be pointed out for (iii) the vibronic spectroscopy, and many others. Implementation of these applications into the package can make Bethe a much more powerful tool.

Meshing highly regular structures: The case of super carbon nanotubes of arbitrary order

Mesh generation is an important step inmany numerical methods.We present the “HierarchicalGraphMeshing” (HGM)method as a novel approach to mesh generation, based on algebraic graph theory.The HGM method can be used to systematically construct configurations exhibiting multiple hierarchies and complex symmetry characteristics. The hierarchical description of structures provided by the HGM method can be exploited to increase the efficiency of multiscale and multigrid methods. In this paper, the HGMmethod is employed for the systematic construction of super carbon nanotubes of arbitrary order, which present a pertinent example of structurally and geometrically complex, yet highly regular, structures. The HGMalgorithm is computationally efficient and exhibits good scaling characteristics. In particular, it scales linearly for super carbon nanotube structures and is working much faster than geometry-based methods employing neighborhood search algorithms. Its modular character makes it conducive to automatization. For the generation of a mesh, the information about the geometry of the structure in a given configuration is added in a way that relates geometric symmetries to structural symmetries. The intrinsically hierarchic description of the resulting mesh greatly reduces the effort of determining mesh hierarchies for multigrid and multiscale applications and helps to exploit symmetry-related methods in the mechanical analysis of complex structures.

Diferencias en la experiencia subjetiva entre depresión unipolar y bipolar

En la depresión unipolar el estado de ánimo predominante es la tristeza y la experiencia corporal es de un cuerpo que se siente más cómodo con la quietud que con la actividad, parecido a la pereza de la vida cotidiana. En la depresión bipolar el estado de ánimo predominante es de apagamiento emocional. La experiencia corporal es de un cuerpo pesado, cansado, un elemento que se interpone entre los deseos de actuar y la realización de las acciones y que se vuelve un obstáculo para el movimiento. Además, en la depresión bipolar hay mayor bradipsíquia, dificultad para concentrarse y desesperanza que en la unipolar. Se realizó una investigación de tipo cualitativo, exploratorio, de las experiencias subjetivas (de primera persona) de un grupo de pacientes con depresión unipolar y bipolar. Se utilizó entrevistas en profundidad de orientación fenomenológica.

Prevalencia de anormalidades estructurales cardiacas en pacientes con enfermedad isquémica. Bogotá 2007 – 2009

Introducción: Las enfermedades cardiovasculares son la causa de muerte más frecuente en el mundo desarrollado, la mayoría de éstas se relacionan con alteraciones de las arterias coronarias, sin embargo un subgrupo de pacientes presentan como causa de isquemia cardiaca alteraciones estructurales. Material y métodos: Estudio Descriptivo. Se utilizó la base de datos recolectada en un servicio de hemodinamia de Bogotá durante dos años. Se aplicaron criterios de inclusión y exclusión y se determinaron cuatro grupos etáreos, a todos los pacientes se les practicó cateterismo cardiaco diagnóstico. Las variables analizadas fueron: diagnóstico de referencia, antecedentes y resultados del cateterismo incluyendo presencia de anomalías estructurales como las valvulopatias, el origen anómalo de las coronarias y los puentes miocárdicos. Para el análisis descriptivo se utilizó reporte de prevalencias y para el análisis de asociaciones se utilizaron tablas de contingencia y el estadístico de prueba Chi cuadrado, no se realizó análisis multivariado debido a que no se encontraron asociaciones estadísticamente significativas. Resultados: La edad promedio de los pacientes fue de 62 años (DS= 10,5), la representación del género masculino fue del 61,7%, la prevalencia de angina estable fue del 61,6%, los 3 antecedentes más prevalentes fueron: hipertensión arterial (41,4%), la hiperlipidemia (19,1%) y la Diabetes Mellitus (17,7%). La prevalencia de las alteraciones estructurales en la población de estudio de manera general fue del 12,9%, y su distribución por tipo fue: 1,4% para puentes miocárdicos, 0,7% para origen anómalo de las arterias coronarias y 10,8% de enfermedad valvular. Conclusiones: Se encontró una asociación entre los antecedentes médicos y la presencia de valvulopatias cardiacas. Se evidenció que el género no tiene relación con la presencia de alteraciones cardíacas a pesar de la mayor participación de hombres en la población de estudio. Las limitantes de este estudio se relacionaron con el tamaño de muestra, debido a la baja prevalencia de las anomalías estructurales medidas.

“Superficial Water Concessions In Light Of The General Theory of the Administrative Act” The Incidence of the Public Law’s Dogmatic Tradition of Public Law Within Environmental Law

This paper seeks the determine the ways in which anomalous decisions derived from the particularization and constitutionalization of environmental law can arise given the general theory of administrative action. This is seen through the lens of a study and characterization of administrative decisions issued by the Regional Autonomous Corporation of Cundinamarca –CAR- within the superficial water concessions procedure. It also discusses the conceptual contents of these licenses.