Laser Spectroscopy: TDLAS instrumentation and NIR analysis of some organic materials

Near-infrared spectroscopy can be a workhorse technique for materials analysis in industries such as agriculture, pharmaceuticals, chemicals and polymers. A near-infrared spectrum represents combination bands and overtone bands that are harmonics of absorption frequencies in the mid-infrared. Near-infrared absorption includes a combination-band region immediately adjacent to the mid-infrared and three overtone regions. All four near-infrared regions contain "echoes" of the fundamental mid-infrared absorptions. For example, vibrations in the mid-infrared due to the C-H stretches will produce four distinct bands in each of the overtone and combination regions. As the bands become more removed from the fundamental frequencies they become more widely separated from their neighbors, more broadened and are dramatically reduced in intensity. Because near-infrared bands are much less intense, more of the sample can be used to produce a spectra and with near-infrared, sample preparation activities are greatly reduced or eliminated so more of the sample can be utilized. In addition, long path lengths and the ability to sample through glass in the near-infrared allows samples to be measured in common media such as culture tubes, cuvettes and reaction bottles. This is unlike mid-infrared where very small amounts of a sample produce a strong spectrum; thus sample preparation techniques must be employed to limit the amount of the sample that interacts with the beam. In the present work we describe the successful the fabrication and calibration of a linear high resolution linear spectrometer using tunable diode laser and a 36 m path length cell and meuurement of a highly resolved structure of OH group in methanol in the transition region A v =3. We then analyse the NIR spectrum of certain aromatic molecules and study the substituent effects using local mode theory

Onset And Characterisation Of Chaos In A Two Dimensional Nonlinear Deterministic Model

Nature is full of phenomena which we call "chaotic", the weather being a prime example. What we mean by this is that we cannot predict it to any significant accuracy, either because the system is inherently complex, or because some of the governing factors are not deterministic. However, during recent years it has become clear that random behaviour can occur even in very simple systems with very few number of degrees of freedom, without any need for complexity or indeterminacy. The discovery that chaos can be generated even with the help of systems having completely deterministic rules - often models of natural phenomena - has stimulated a lo; of research interest recently. Not that this chaos has no underlying order, but it is of a subtle kind, that has taken a great deal of ingenuity to unravel. In the present thesis, the author introduce a new nonlinear model, a ‘modulated’ logistic map, and analyse it from the view point of ‘deterministic chaos‘.

Study of Synchronisalion and Control of Chaos in Directly Modulated Semiconductor Lasers

Chaos is a subject oftopical interest and, studied in great detail in relation to its relevance in almost all branches of science, which include physical, chemical, and biological fields. Chaos in the literal sense signifies utter confusion, but the scientific community has differentiated chaos as deterministic chaos and white noise. Deterministic chaos implies the complex behaviour of systems, which are governed by deterministic laws. Behaviour of such systems often become unpredictable in the long run. This unpredictability arises from the sensitivity of the system to its initial conditions. The essential requirement for ‘sensitivity to initial condition’ is nonlinearity of the system. The only method for determining the future of such systems is numerically simulating its final state from a set ofinitial conditions. Synchronisation

Raman and infrared spectral analysis of thallium niobyl phosphates: Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7

Raman and infrared spectra of Tl2NbO2PO4, Tl3NaNb4O9(PO4)2 and TlNbOP2O7 are reported. The observed bands are assigned in terms of vibrations of NbO6 octahedra and PO4 tetrahedra in the first two compounds and in terms of NbO6 octahedra and P2O7 4− anion in the third compound. The NbO6 octahedra in all the title compounds are found to be corner-shared and distorted. The higher wavenumber values of the ν1 (NbO6) mode and other stretching modes indicate that the NbO6 octahedra in them are distorted in the order TlNbOP2O7 > Tl2NbO2PO4 > Tl3NaNb4O9(PO4)2. The splitting of the ν3 (PO4) mode indicates that PO4 tetrahedra is distorted more in Tl2NbO2PO4 than in Tl3NaNb4O9(PO4)2. The symmetry of P2O7 4− anion in TlNbOP2O7 is lowered. Bands indicate that the P–O–P bridge in the above compound has a bent P–O–P bridge configuration

Raman and FTIR studies of the structural aspects of Nasicon-type crystals; AFeTi(PO4)3 [A ¼ Ca, Cd]

Raman and FTIR spectra of CaFeTi(PO4)3 and CdFeTi(PO4)3 are recorded and analyzed. The observed bands are assigned in terms of vibrations of TiO6 octahedra and PO4 tetrahedra. The symmetry of TiO6 octrahedra and PO4 tetrahedra is lowered from their free ion symmetry. The presence of Fe3+ ion disrupts the Ti–O–P–O–Ti chain and leads to the distortion of TiO6 octrahedra and PO4 tetrahedra. The PO4 3 tetrahedra in both crystals are linearly distorted. The covalency bonding factor of PO4 3 polyanion of both the crystals are calculated from the Raman spectra and compared to that of other Nasicon-type systems. The numerical values of covalency bonding factor indicates that there is a reduction in redox energy and cell voltage and is attributed to strong covalency of PO4 3 polyanionin

Vibrational spectroscopic studies of Guanidinium metal (MII) sulphate hexahydrates [MII = Co, Fe, Ni]

The Raman and FTIR spectra of [C(NH2)3]2M(SO4)2 ·6H2O (withM= Co, Fe, Ni) were recorded and analysed. The observed spectral bands are assigned in terms of vibrations of guanidinium ions, sulphate groups and water molecules. The analysis shows that the sulphate tetrahedra are distorted from their free state symmetry Td to C1. This is attributed to the presence of hydrogen bonds from water molecules. The order of distortion of the metal oxygen octahedra influenced the distortion of the sulphate tetrahedra. The appearance of 1– 3 modes of water molecules above 3300 cm−1 indicates the presence of weak hydrogen bonds

Infrared and polarized Raman spectra of Cu(HSeO3)2 • H20 single crystal

Infrared and polarized Raman spectra of Cu(HSeO3) 2 - H20 single crystal have been recorded and analysed. The appearance of non-degenerate Se-OH stretching vibrations in the ~x: and ~y: polarizations of Raman spectra indicate distortion of the HSeO~- ion in the Cu(HSeO3)2 - H20 crystal. The low wavenumber values obtained for the symmetric and asymmetric stretching vibrations of the HSeO 3 ion are consistent with the strong hydrogen bonding and the influence of Jahn-Teller distortion as predicted in X-ray diffraction data. The shifting of the stretching and bending vibrations of the hydroxyl groups and water molecules from the free state values also confirms the strong hydrogen bonding in this crystal. Broad bands observed for both stretching and bending regions become sharp in the Raman spectrum recorded at 77 K. A doublet appears for the Se-OH stretching mode at this temperature indicating the settling of protons in an ordered position and the absence of intrabond proton tunnelling

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3 − and H2O vibrations. Additional bands obtained in the region of 3 and 1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of 3 modes, since the BrO3 − ion occupies a site of lower symmetry. The appearance 1 mode of BrO3 − anion at a lower wavenumber (771 cm−1) is attributed to the attachment of hydrogen to the BrO3 − anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 · 3H2O structure is confirmed. The lifting of degeneracy of 4 mode indicates that the symmetry of BrO3 − anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77–523 K for various temperatures. A small structural rearrangement takes place in BrO3 − ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3 − ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

Femtosecond dynamics of molecular and cluster ionization and fragmentation

The real-time dynamics of molecular (Na_2 . Na_3) and cluster Na_n (n=4-2l) multiphoton ionization and -fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Wave packet motion in the dimer Na_2 reveals two independent multiphoton ionization processes while the higher dimensional motion in the trimer Na_3 reflects the chaotic vibrational motion in this floppy system. The first studies of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na^*_n) ) with femtosecond laser pulses give a striking illustration of the transition from "molecule-like" excitations to "surfaceplasma"-like resonances for increasing cluster sizes. Time-resolved fragmentation of cluster ions Na_n^* indicate that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Electronic origin of bond softening and hardening in femtosecond-laser-excited magnesium

Many ultrafast structural phenomena in solids at high fluences are related to the hardening or softening of particular lattice vibrations at lower fluences. In this paper we relate femtosecond-laser-induced phonon frequency changes to changes in the electronic density of states, which need to be evaluated only in the electronic ground state, following phonon displacement patterns. We illustrate this relationship for a particular lattice vibration of magnesium, for which we—surprisingly—find that there is both softening and hardening as a function of the femtosecond-laser fluence. Using our theory, we explain these behaviours as arising from Van Hove singularities: We show that at low excitation densities Van Hove singularities near the Fermi level dominate the change of the phonon frequency while at higher excitations Van Hove singularities that are further away in energy also become important. We expect that our theory can as well shed light on the effects of laser excitation of other materials.

Structural Dynamics Model of a Cartesian Robot

Methods are developed for predicting vibration response characteristics of systems which change configuration during operation. A cartesian robot, an example of such a position-dependent system, served as a test case for these methods and was studied in detail. The chosen system model was formulated using the technique of Component Mode Synthesis (CMS). The model assumes that he system is slowly varying, and connects the carriages to each other and to the robot structure at the slowly varying connection points. The modal data required for each component is obtained experimentally in order to get a realistic model. The analysis results in prediction of vibrations that are produced by the inertia forces as well as gravity and friction forces which arise when the robot carriages move with some prescribed motion. Computer simulations and experimental determinations are conducted in order to calculate the vibrations at the robot end-effector. Comparisons are shown to validate the model in two ways: for fixed configuration the mode shapes and natural frequencies are examined, and then for changing configuration the residual vibration at the end of the mode is evaluated. A preliminary study was done on a geometrically nonlinear system which also has position-dependency. The system consisted of a flexible four-bar linkage with elastic input and output shafts. The behavior of the rocker-beam is analyzed for different boundary conditions to show how some limiting cases are obtained. A dimensional analysis leads to an evaluation of the consequences of dynamic similarity on the resulting vibration.

Forecasting Global Temperature Variations by Neural Networks

Global temperature variations between 1861 and 1984 are forecast usingsregularization networks, multilayer perceptrons and linearsautoregression. The regularization network, optimized by stochasticsgradient descent associated with colored noise, gives the bestsforecasts. For all the models, prediction errors noticeably increasesafter 1965. These results are consistent with the hypothesis that thesclimate dynamics is characterized by low-dimensional chaos and thatsthe it may have changed at some point after 1965, which is alsosconsistent with the recent idea of climate change.s

A mixed H2/H∞-based semiactive control for vibration mitigation in flexible structures

In this paper, we address this problem through the design of a semiactive controller based on the mixed H2/H∞ control theory. The vibrations caused by the seismic motions are mitigated by a semiactive damper installed in the bottom of the structure. It is meant by semiactive damper, a device that absorbs but cannot inject energy into the system. Sufficient conditions for the design of a desired control are given in terms of linear matrix inequalities (LMIs). A controller that guarantees asymptotic stability and a mixed H2/H∞ performance is then developed. An algorithm is proposed to handle the semiactive nature of the actuator. The performance of the controller is experimentally evaluated in a real-time hybrid testing facility that consists of a physical specimen (a small-scale magnetorheological damper) and a numerical model (a large-scale three-story building)

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