7 resultados para Transition-state Theory

em Cochin University of Science


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The thesis presents the dynamics of a polymer chain under tension. It includes existing theories of polymer fracture, important theories of reaction rates, the rate using multidimensional transition state theory and apply it to the case of polyethylene etc. The main findings of the study are; the life time of the bond is somewhat sensitive to the potential lead to rather different answers, for a given potential a rough estimate of the rate can be obtained by a simples approximation that considers the dynamics of only the bond that breaks and neglects the coupling to neighboring bonds. Dynamics of neighboring bonds would decrease the rate, but usually not more than by one order of magnitude, for the breaking of polyethylene, quantum effects are important only for temperatures below 150K, the lifetime strongly depends on the strain and as the strain varies over a narrow range, the life varies rapidly from 105 seconds to 10_5 seconds, if we change one unit of the polymer by a foreign atom, say by one sulphure atom, in the main chain itself, by a weaker bond, the rate is found to increase by orders of magnitude etc.

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The objective of this thesis is to study the time dependent behaviour of some complex queueing and inventory models. It contains a detailed analysis of the basic stochastic processes underlying these models. In the theory of queues, analysis of time dependent behaviour is an area.very little developed compared to steady state theory. Tine dependence seems certainly worth studying from an application point of view but unfortunately, the analytic difficulties are considerable. Glosod form solutions are complicated even for such simple models as M/M /1. Outside M/>M/1, time dependent solutions have been found only in special cases and involve most often double transforms which provide very little insight into the behaviour of the queueing systems themselves. In inventory theory also There is not much results available giving the time dependent solution of the system size probabilities. Our emphasis is on explicit results free from all types of transforms and the method used may be of special interest to a wide variety of problems having regenerative structure.

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The thesis deals with certain quantum field systems exhibiting spontaneous symmetry breaking and their response to temperature. These models find application in diverse branches such as particle physics, solid state physics and non~linear optics. The nature of phase transition that these systems may undergo is also investigated. The thesis contains seven chapters. The first chapter is introductory and gives a brief account of the various phenomena associated with spontaneous symmetry breaking. The chapter closes with anote on the effect of temperature on quantum field systems. In chapter 2, the spontaneous symmetry breaking phenomena are reviewed in more detail. Chapter 3, deals with the formulation of ordinary and generalised sine-Gordon field theories on a lattice and the study of the nature of phase transition occurring in these systems. In chapter 4, the effect of temperature on these models is studied, using the effective potential method. Chapter 5 is a continuation of this study for another model, viz, the m6 model. The nature of phase transition is also studied. Chapters 5 and 6 constitute a report of the investigations on the behaviour of coupling constants under thermal excitation D1 $4 theory, scalar electrodynamics, abelian and non-abelian gauge theories

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Coordination chemistry of schiff bases is of considerable interest due to their various magnetic, catalytic and biological applications. Here it describes the spectral characterization of schiff bases and its Mn (II), Cu (II) and Ni (II) complexes. Then synthesis and spectral characterization of Zn (II), Cd (II) and Co (II) complexes of schiff base derived from 3-Formylsalicilic Acid and 1,3-diaminopropane. Then it discusses the synthesis and spectral studies of Copper (II) complexes of 2-Hydroxyacetophenone N-phenyl semicarbazone. Finally it discusses the synthesis and spectral characterization of Co (III) complexes of salicylaldehyde N-phenyl semicarbazone. The preparation and characterization of Cobalt (III) complexes of salicylaldehyde, N-phenylthiosemicarbazone containing hetrocyclic bases phenalthroline and bipyridine. Thiocyanate, azide and perchlorate ions act as coligands. Elemental analysis suggests +3 state for Cobalt. HNMR, IR and UV-visible spectra characterize the complexes.

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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.

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This thesis comprises five chapters including the introductory chapter. This includes a brief introduction and basic definitions of fuzzy set theory and its applications, semigroup action on sets, finite semigroup theory, its application in automata theory along with references which are used in this thesis. In the second chapter we defined an S-fuzzy subset of X with the extension of the notion of semigroup action of S on X to semigroup action of S on to a fuzzy subset of X using Zadeh's maximal extension principal and proved some results based on this. We also defined an S-fuzzy morphism between two S-fuzzy subsets of X and they together form a category S FSETX. Some general properties and special objects in this category are studied and finally proved that S SET and S FSET are categorically equivalent. Further we tried to generalize this concept to the action of a fuzzy semigroup on fuzzy subsets. As an application, using the above idea, we convert a _nite state automaton to a finite fuzzy state automaton. A classical automata determine whether a word is accepted by the automaton where as a _nite fuzzy state automaton determine the degree of acceptance of the word by the automaton. 1.5. Summary of the Thesis 17 In the third chapter we de_ne regular and inverse fuzzy automata, its construction, and prove that the corresponding transition monoids are regular and inverse monoids respectively. The languages accepted by an inverse fuzzy automata is an inverse fuzzy language and we give a characterization of an inverse fuzzy language. We study some of its algebraic properties and prove that the collection IFL on an alphabet does not form a variety since it is not closed under inverse homomorphic images. We also prove some results based on the fact that a semigroup is inverse if and only if idempotents commute and every L-class or R-class contains a unique idempotent. Fourth chapter includes a study of the structure of the automorphism group of a deterministic faithful inverse fuzzy automaton and prove that it is equal to a subgroup of the inverse monoid of all one-one partial fuzzy transformations on the state set. In the fifth chapter we define min-weighted and max-weighted power automata study some of its algebraic properties and prove that a fuzzy automaton and the fuzzy power automata associated with it have the same transition monoids. The thesis ends with a conclusion of the work done and the scope of further study.

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One of the interesting consequences of Einstein's General Theory of Relativity is the black hole solutions. Until the observation made by Hawking in 1970s, it was believed that black holes are perfectly black. The General Theory of Relativity says that black holes are objects which absorb both matter and radiation crossing the event horizon. The event horizon is a surface through which even light is not able to escape. It acts as a one sided membrane that allows the passage of particles only in one direction i.e. towards the center of black holes. All the particles that are absorbed by black hole increases the mass of the black hole and thus the size of event horizon also increases. Hawking showed in 1970s that when applying quantum mechanical laws to black holes they are not perfectly black but they can emit radiation. Thus the black hole can have temperature known as Hawking temperature. In the thesis we have studied some aspects of black holes in f(R) theory of gravity and Einstein's General Theory of Relativity. The scattering of scalar field in this background space time studied in the first chapter shows that the extended black hole will scatter scalar waves and have a scattering cross section and applying tunneling mechanism we have obtained the Hawking temperature of this black hole. In the following chapter we have investigated the quasinormal properties of the extended black hole. We have studied the electromagnetic and scalar perturbations in this space-time and find that the black hole frequencies are complex and show exponential damping indicating the black hole is stable against the perturbations. In the present study we show that not only the black holes exist in modified gravities but also they have similar properties of black hole space times in General Theory of Relativity. 2 + 1 black holes or three dimensional black holes are simplified examples of more complicated four dimensional black holes. Thus these models of black holes are known as toy models of black holes in four dimensional black holes in General theory of Relativity. We have studied some properties of these types of black holes in Einstein model (General Theory of Relativity). A three dimensional black hole known as MSW is taken for our study. The thermodynamics and spectroscopy of MSW black hole are studied and obtained the area spectrum which is equispaced and different thermo dynamical properties are studied. The Dirac perturbation of this three dimensional black hole is studied and the resulting quasinormal spectrum of this three dimensional black hole is obtained. The different quasinormal frequencies are tabulated in tables and these values show an exponential damping of oscillations indicating the black hole is stable against the mass less Dirac perturbation. In General Theory of Relativity almost all solutions contain singularities. The cosmological solution and different black hole solutions of Einstein's field equation contain singularities. The regular black hole solutions are those which are solutions of Einstein's equation and have no singularity at the origin. These solutions possess event horizon but have no central singularity. Such a solution was first put forward by Bardeen. Hayward proposed a similar regular black hole solution. We have studied the thermodynamics and spectroscopy of Hay-ward regular black holes. We have also obtained the different thermodynamic properties and the area spectrum. The area spectrum is a function of the horizon radius. The entropy-heat capacity curve has a discontinuity at some value of entropy showing a phase transition.