Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Studies on molecular structure and properties using microwave and infrared spectral data

The major objective of the thesis is essentially to evolve and apply certain computational procedures to evaluate the structure and properties of some simple polyatomic molecules making use of spectroscopic data available from the literature. It must be said that though there is dwindling interest in recent times in such analyses, there exists tremendous scope and utility for attempting such calculations as the precision and reliability of'experimental techniques in spectroscopy have increased vastly due to enormous sophistication of the instruments used for these measurements. In the present thesis an attempt is made to extract maximum amount of information regarding the geometrical structure and interatmic forces of simple molecules from the experimental data on microwave and infrared spectra of these molecules

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

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Spectral, Structural And Biological Studies Of Some Metal Complexes Of ‘Nsubstituted 2-Benzoylpyridine Thiosemicarbazones

Aqua complex ions of metals must have existed since the appearance of water on the earth, and the subsequent appearance of life depended on, and may even have resulted from the interaction of metal ions with organic molecules. Studies on the coordinating ability of metal ions with other molecules and anions culminated in the theories of/\lfred Werner. Thereon the progress in the studies of metal complex chemistry was rapid. Many factors, like the utility and economic importance of metal chemistry, the intrinsic interest _in many of the compounds and the intellectual challenge of the structural problems to be solved, have contributed to this rapid progress. X—ray diffraction studies further accelerated the progress. The work cited in this thesis was carried out by the author in the Department of Applied Chemistry during 2001-2004. The primary aim of these investigations was to synthesise and characterize some transition metal complexes of 2-benzoylpyridine N(4)-substituted thiosemicarbazones and to study the antimicrobial activities of the ligands and their metal complexes. The work is divided into eight chapters

Vibrational spectroscopic studies of FeClMoO4, Na2MoO4 and Na2MoO4·2H2O:D2O

FTIR and Raman spectra of FeClMoO4 single crystal and polycrystalline Na2MoO4, Na2MoO4·2H2O and Na2MoO4·2D2O are recorded and analysed. The band positions for different modes suggest that MoO4 tetrahedron is more distorted in FeClMoO4. The larger splitting observed for the bending modes and partial retention of degeneracy of the asymmetric stretching mode indicate that angular distortion is greater than liner distortion in MoO4 2 ion in FeClMoO4 confirming x-ray data. The non-appearance of the n1 and n2 modes in the IR and partial retention of the degeneracies of various modes show that MoO4 2 ion retains Td symmetry in Na2MoO4. Wavenumber values of the n1 mode indicate that the distortion of MoO4 tetrahedra in the four crystals are in the order FeClMoO4\ Na2MoO4·2H2O\Na2MoO4·2D2O\Na2MoO4. The water bands suggest the presence of two crystallographically distinct water molecules in Na2MoO4·2H2O. They form strong hydrogen bonds

Overtone Spectra of 1,2-Dichloro-And Dibromo-Ethanes in the Near Infrared Region

The vibrational overtone spectra 0f the liquid phase 1,2-dichloroethane and 1,2-dibromoethane in the spectral regions of CH stretching local mode overtones corresponding to delta v CH= = 2 to delta v CH=5 are reported. The observed spectral features are assigned using the local mode model. LocaI mode frequencies WCH and diagonal local mode anharmonicities XCH are obtained from an analysis of the spectra. The local-local combinations observed are interpreted on the basis of a coupled CH oscillator model hamiltonian. Local-normal combinations show complex structures and their possible assignments are given.

Overtone spectra of styrene and polystyrene in the visible and near infrared regions

Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

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

Optical properties of phthalocyanine molecules in cyano acrylate polymer matrix

Optical absorption and emission spectral studies of various phthalocyanine molecules, viz., LaPc, NdPc, SmPc, EuPc, CuPc and ZnPc in a polymer matrix of cyano acrylate are reported for the first time. All the absorption spectra show an intense B band (Soret) in the UV region followed by a weaker Q band in the visible region. The positions of the Q and B bands are found to have dependence on the metallic substitution. Values of the important spectral parameters, viz., molar extinction coefficient (ϵ), oscillator strength (f), radiative transition rate and decay time of the excited singlet state are also presented and compared with other solid matrices. The recorded fluorescence spectrum shows two broad emission bands in the case of NdPc, whereas for ZnPc only a very weak band is observed. The absence of emission bands for the other metallated phthalocyanines is attributed to increased spin orbit interaction and intersystem crossing.

NIR to UV absorption spectra and the optical constants of phthalocyanines in glassy medium

Optical absorption studies of phthalocyanines (Pc-s) in borate glass matrix have been reported for the first time. Measurements have been done corresponding to photon energies between 1.1 and 6.2 eV for free base, manganese, iron, nickel, molybdenum, cobalt and copper phthalocyanines. Several new discrete transitions are observed in the UV–vis region of the spectra in addition to a strong continuum component of absorption in the IR region. Values of some of the important optical constants viz. absorption coefficient (α), molar extinction coefficient (ε), absorption cross-section (σa), band width (Δλ), electric dipole strength (q2) and oscillator strength (f) for the relevant electronic transitions are also presented. All the data reported for Pc-s in the new matrix have been compared with those corresponding to solution, vapor and thin film media.

Optical properties of porphyrins in borate glassy matrix

Optical properties of free and substituted porphyrins (PP) doped borate glass matrix are reported for the first time. Absorption spectral measurements of H2TPP, CdTPP, MgTPP and ZnTPP doped borate glass matrix have been made in the 200–1100 nm region and the spectra obtained are analyzed to obtain the optical bandgap (Eg) and other important spectral parameters viz. oscillator strength (f), molar extinction coefficient (ε), electric dipole strength (q2), absorption cross-section (σa) and molecular concentration (N). Intense fluorescence was observed in the region 668–685 nm for CdTPP, ZnTPP and MgTPP doped matrices, whereas no such fluorescence was observed in H2TPP doped matrix. Fluorescence intensity was observed to be almost similar in all the metallated porphyrine matrices. Fluorescence bandwidth (Δλ), decay time (τ), stimulated emission cross-section (σ) and optical gain (G) of the principal fluorescence transitions corresponding to the Q-band excitation were also evaluated and discussed.

Laser induced thermal lens and near infrared absorption studies of ch overtones in some organic compounds

Vibrational overtone spectroscopy of X-H (X=C,N,O) containing molecules is an area of recent interest. The spectroscopic studies of higher vibrational levels yield valuable informations, regarding,the molecular structure, intra- and inter-molecular interactions, radiationless transitions, intra-molecular vibrational relaxations, multiphoton excitations and chemical reactivities, which cannot be z obtained by other spectroscopic methods. This thesis presents the results of experimental investigations on the overtone spectra of some organic compounds in the liquid phase for the characterization of CH bonds. The spectra in the fifth overtone region (1fiV=6) are recorded using a dual beam thermal lens setup and the lower overtones (.AV=2-5) are recorded spectrophotometrically.The thesis is presented in six chapters.

Development of selected electro-active polymer-ceramic nanocomposites as pyroelectric thermal/infrared detector materials

The present work emphasises on the synthesis and characterization of electro-active polymer-ceramic nanocomposites which can be used for pyroelectric thermal/infrared detection applications. Two sets of samples belong to polymer-microcrystalline composites have also been investigated in the work. The polymers used in the work have been commercially available ones, but the nanoceramics have been synthesized following simple chemical routes and aqueous organic gel routes. After characterizing the nanoceramics for their structure by powder XRD, they have been dispersed in liquid polymer and sonicated for uniform dispersion. The viscous mixture so formed was cast in the form of films for experimentation. Samples with volume fraction of the ceramic phase varied from 0 to 0.25 have been prepared. Solution growth was followed to prepare microcrystalline samples for the polymer-microcrystalline composites. The physical properties that determine the pyroelectric sensitivity of a material are dielectric constant, dielectric loss, pyroelectric coefficient, thermal conductivity and specific heat capacity. These parameters have been determined for all the samples and compositions reported in this work.The pyroelectric figures of merit for all the samples were determined. The pyroelectric figures of merit that determine the pyroelectric sensitivity of a material are current sensitivity, voltage responsivity and detectivity. All these have been determined for each set of samples and reported in the thesis. In order to assess the flexibility and mouldability of the composites we have measured the Shore hardness of each of the composites by indentation technique and compared with the pyroelectric figures of merit. Some important factors considered during the material fabrication stages were maximum flexibility and maximum figures of merit for pyroelectric thermal/IR detection applications. In order to achieve these goals, all the samples are synthesized as composites of polymers and nano/microcrystalline particles and are prepared in the form of freestanding films. The selected polymer matrices and particle inclusions possess good pyroelectric coefficients, low thermal and dielectric properties, so that good pyroelectric figures of merit could be achieved. The salient features of the work include the particle size of the selected ceramic materials. Since they are in nanometer size it was possible to achieve high flexibility and moldability with high figures of merit for even low volume fractions of inclusions of the prepared nanocrystalline composites. In the case of microcrystalline TGS and DTGS, their composites in PU matrix protect them from fragility and humidity susceptibility and made them for environmental friendly applications.