Photothermal Investigations on Certain Plasma Polymerized Thin Films and Near IR Overtone Studies of Some Organic Molecules

Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and is detected using a position sensitive detector and its output is fed to a lock-in amplifier from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

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.

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

“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

C-H and C-D interbond coupling in CHDCl2

Laser photoacoustic spectra of vapour phase CHDCl2 reveal the presence of an interaction which has been ascribed to interbond coupling between C-H and C-D local modes. The absolute value of the interbond coupling parameter for the CHD group, determined from a fit of a model local mode hamiltonian to the experimental data, is shown to be given approximately by the geometric mean of the interbond coupling parameters of the CH2 and CD2 groups recently derived from similar studies of CH2Cl2 and CD2Cl2. Such behaviour is understood in terms of a simple analysis in which kinetic coupling effects dominate. It is suggested that C-H stretch/bend Fermi resonance is responsible for some weaker features in the spectra and modelling calculations are described which allow an order of magnitude estimate of the size of the coupling parameter involved.

Calculated rotational and rovibrational spectra of D2S and HDS

Rovibrational energy levels, transition frequencies, and linestrengths are computed variationally for the sulfur hydrides D2S and HDS, using ab initio potential energy and dipole surfaces. Wave-numbers for the pure rotational transitions agree to within 0.2 cm−1 of the experimental lines. For the fundamental vibrational transitions, the band origins for D2S are 860.4, 1900.6, and 1912.0 cm−1 for ν2, ν1, and ν3, respectively, compared with the corresponding experimental values of 855.4, 1896.4, and 1910.2 cm−1. For HDS, we compute ν2 to be 1039.4 cm−1, compared with the experimental value of 1032.7 cm−1. The relative merits of local and normal mode descriptions for the overtone stretching band origins are discussed. Our results confirm the local mode nature of the H2S, D2S, and HDS system.

Understanding spectra of highly excited vibrational states

Some of the characteristics of high overtone spectra observed in the near infrared are discussed, particularly in relation to local mode effects, the increasing density of states, and the effect of inter-state resonances and intramolecular vibrational redistribution.

Nanofiber-based spectroscopy of organic molecules

This thesis reports on the experimental realization of nanofiber-based spectroscopy of organic molecules. The light guided by subwavelength diameter optical nanfibers exhibits a pronounced evanescent field surrounding the fiber which yields high excitation and emission collection efficiencies for molecules on or near the fiber surface.rnThe optical nanofibers used for the experiments presented in this thesis are realized as thernsub-wavelength diameter waist of a tapered optical fiber (TOF). The efficient transfer of thernlight from the nanofiber waist to the unprocessed part of the TOF depends critically on therngeometric shape of the TOF transitions which represent a nonuniformity of the TOF. Thisrnnonuniformity can cause losses due to coupling of the fundamental guided mode to otherrnmodes which are not guided by the taper over its whole length. In order to quantify the lossrnfrom the fundamental mode due to tapering, I have solved the coupled local mode equationsrnin the approximation of weak guidance for the three layer system consisting of fiber core andrncladding as well as the surrounding vacuum or air, assuming the taper shape of the TOFsrnused for the experiments presented in this thesis. Moreover, I have empirically studied therninfluence of the TOF geometry on its transmission spectra and, based on the results, I haverndesigned a nanofiber-waist TOF with broadband transmission for experiments with organicrnmolecules.rnAs an experimental demonstration of the high sensitivity of nanofiber-based surface spectroscopy, I have performed various absorption and fluorescence spectroscopy measurements on the model system 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA). The measured homogeneous and inhomogeneous broadening of the spectra due to the interaction of the dielectric surface of the nanofiber with the surface-adsorbed molecules agrees well with the values theoretically expected and typical for molecules on surfaces. Furthermore, the self-absorption effects due to reasorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist have been analyzed and quantified. With time-resolved measurements, the reorganization of PTCDA molecules to crystalline films and excimers can be observed and shown to be strongly catalyzed by the presence of water on the nanofiber surface. Moreover, the formation of charge-transfer complexes due to the interaction with localized surface defects has been studied. The collection efficiency of the molecular emission by the guided fiber mode has been determined by interlaced measurements of absorption and fluorescence spectra to be about 10% in one direction of the fiber.rnThe high emission collection efficiency makes optical nanofibers a well-suited tool for experiments with dye molecules embedded in small organic crystals. As a first experimental realization of this approach, terrylene-doped para-terphenyl crystals attached to the nanofiber-waist of a TOF have been studied at cryogenic temperatures via fluorescence and fluorescence excitation spectroscopy. The statistical fine structure of the fluorescence excitation spectrum for a specific sample has been observed and used to give an estimate of down to 9 molecules with center frequencies within one homogeneous width of the laser wavelength on average for large detunings from resonance. The homogeneous linewidth of the transition could be estimated to be about 190MHz at 4.5K.

Local lifetime engineering in 600V pin diode using mix-mode simulation

This paper reports a detailed analysis of the effect of local lifetime killing (LLK) within the drift region on the reverse recovery (RR) characteristics and on-state performance of 600V Silicon PiN diodes. The paper also discusses the influence of the measurement circuit on the reverse recovery of the high voltage diodes and it proposes a simple and effective mix-mode simulation tool for an accurate assessment of the diode performance in reverse recovery mode. © 2013 IEEE.

‘The health-location connection’: using GIS and social media on smartphones to track engagement with the Local urban environment for work, recreation, and physical activity

A technologically innovative study was undertaken across two suburbs in Brisbane, Australia, to assess socioeconomic differences in women's use of the local environment for work, recreation, and physical activity. Mothers from high and low socioeconomic suburbs were instructed to continue with usual daily routines, and to use mobile phone applications (Facebook Places, Twitter, and Foursquare) on their mobile phones to ‘check-in’ at each location and destination they reached during a one-week period. These smartphone applications are able to track travel logistics via built-in geographical information systems (GIS), which record participants’ points of latitude and longitude at each destination they reach. Location data were downloaded to Google Earth and excel for analysis. Women provided additional qualitative data via text regarding the reasons and social contexts of their travel. We analysed 2183 ‘check-ins’ for 54 women in this pilot study to gain quantitative, qualitative, and spatial data on human-environment interactions. Data was gathered on distances travelled, mode of transport, reason for travel, social context of travel, and categorised in terms of physical activity type – walking, running, sports, gym, cycling, or playing in the park. We found that the women in both suburbs had similar daily routines with the exception of physical activity. We identified 15% of ‘check-ins’ in the lower socioeconomic group as qualifying for the physical activity category, compared with 23% in the higher socioeconomic group. This was explained by more daily walking for transport (1.7kms to 0.2kms) and less car travel each week (28.km to 48.4kms) in the higher socioeconomic suburb. We ascertained insights regarding the socio-cultural influences on these differences via additional qualitative data. We discuss the benefits and limitations of using new technologies and Google Earth with implications for informing future physical and social aspects of urban design, and health promotion in socioeconomically diverse cities.

The Enamovirus P0 protein is a silencing suppressor which inhibits local and systemic RNA silencing through AGO1 degradation

The P0 protein of poleroviruses and P1 protein of sobemoviruses suppress the plant's RNA silencing machinery. Here we identified a silencing suppressor protein (SSP), P0PE, in the Enamovirus Pea enation mosaic virus-1 (PEMV-1) and showed that it and the P0s of poleroviruses Potato leaf roll virus and Cereal yellow dwarf virus have strong local and systemic SSP activity, while the P1 of Sobemovirus Southern bean mosaic virus supresses systemic silencing. The nuclear localized P0PE has no discernable sequence conservation with known SSPs, but proved to be a strong suppressor of local silencing and a moderate suppressor of systemic silencing. Like the P0s from poleroviruses, P0PE destabilizes AGO1 and this action is mediated by an F-box-like domain. Therefore, despite the lack of any sequence similarity, the poleroviral and enamoviral SSPs have a conserved mode of action upon the RNA silencing machinery. © 2012 Elsevier Inc.