A comparative study of energy transfer in dye mixtures in monomer and polymer matrices under pulsed laser excitation

This study was conducted to identify the concentration dependence of the operating wavelengths and the relative intensities in which a dye mixture doped polymer optical fibre can operate. A comparative study of the radiative and Forster type energy transfer processes in Coumarin 540:Rhodamine 6G, Coumarin 540:Rhodamine B and Rhodamine 6G:Rhodamine B in methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) was done by fabricating a series of dye mixture doped polymer rods which have two emission peaks with varying relative intensities. These rods can be used as preforms for the fabrication of polymer optical fibre amplifiers operating in the multi-wavelength regime. The 445 nm line from an Nd:YAG pumped optical parametric oscillator (OPO) was used as the excitation source for the first two dye pairs and a frequency doubled Nd:YAG laser emitting at 532 nm was used to excite the Rh 6G:Rh B pair. The fluorescence lifetimes of the donor molecule in pure form as well as in the mixtures were experimentally measured in both monomer and polymer matrices by time-correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed. It was found that radiative energy transfer mechanisms are more efficient in all the three dye pairs in liquid and solid matrices.

Excitation wavelength dependence of energy transfer in dye mixture doped polymer optical fibre preforms

Dependence of energy transfer parameters on excitation wavelength has been investigated in poly (methyl methacrylate) (PMMA) optical fibre preforms doped with C 540:Rh B dye mixture by studying the fluorescence intensity and the lifetime variations. A fluorescence spectrophotometer was used to record the excitation spectra of the samples for the emission wavelengths 495 and 580 nm. The fluorescence emission from the polymer rods was studied at four specific excitation wavelengths viz; 445, 465, 488 and 532 nm. The fluorescence lifetime of the donor molecule was experimentally measured in polymer matrix by time correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed for three excitation wavelengths. It was found that any change in the excitation wavelength leads to significant variations in the quenching characteristics, which in turn affect the calculated energy transfer parameters.

Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes

The thesis entitled: ‘Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes’ is divided into 5 chapters.In Chapter 1, the fundamental concepts of Diels-Alder reaction, di-r:methane rearrangement and energy transfer process in organic photochemistry is discussed.Chapter 2 presents the synthesis of 9-olefin appended anthracenes and bisanthracenes. The target of synthesising various bridgehead olefin appended dibenzobarrelenes and some novel bisdibenzobarrelenes, led us to the synthesis of the appropriate alkenylanthracenes and bisanthracenes as precursor molecules. Diels-Alder reaction was the synthetic tool for the preparation of the target olefin appended dibenzobarrelenes and bisdibenzobarrelenes. This chapter attempts to throw light on our endeavours in synthesising the various 9-alkenylanthracenes and bisanthracenes.Chapter 3 deals with the synthesis of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Ever since the discovery of di-It-methane rearrangement dibenzobarrelenes, tailored with dijferent substituents at various positions have always been a tool to photochemists in unravelling the mechanisms of light induced reactions. Our intention of analysing the role of a It-moiety at the bridgehead position of the dibenzobarrelene, was synthetically envisaged via the Diels-Alder reaction. Bisdibenzobarrelenes were synthesised through tandem Diels-Alder reaction. Various alkenylanthracenes and bisanthracenes were employed as dienes and the dienophiles used were dimethyl acetylenedicarboxylate and dibenzoylacetylene. In this chapter, we report our venture in synthesising the various olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Chapter 4 describes the preliminary time-resolved fluorescence studies of some olefin appended dibenzobarrelenes and bisdibenzobarrelenes.To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes.Chapter 5 portrays the photochemistry of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Dibenzocyclooctatetraene and dibenzosemibullvalene are the photoproducts obtained respectively through the singlet excited state and the triplet excited state of dibenzobarrelenes. Chemical literature shows evidences of the photoreactivity of dibenzobarrelenes generating both the singlet and triplet mediated photoproducts, in a single photoreaction. Our research target in synthesising various bridgehead olefin appended dibenzobarrelenes and bisdibenzobarrelenes, was based on the perception that olefins are eflicient triplet quenchers, thereby quenching intramolecularly the triplet excited state of the barrelenes. A It-moiety at the bridgehead position of the dibenzobarrelene, creates a tetra tr-methane system, which similar to a 6li—7l' or tri-tr-methane systems, could be the fertile ground for interesting photochemical rearrangements. Our attempts in deciphering the photochemistry of the olefin appended dibenzobarrelenes and bisdibenzobarrelenes is the substance of this chapter.

Characteristics of two-photon absorption in methanol solutions of Rhodamine 6G using laser induced pulsed photoacoustics

Two-photon absorption in methanol solutions of Rhodamine 6G is investigated by photoacoustics using the second harmonic of a pulsed Nd:YAG laser. Competition between one-photon and two-photon processes is observed, depending critically on the sample concentration and input light flux.

Studies on Two-Photon Absorption of Aniline Using Thermal Lens Effect

Two-photon absorption spectrum of aniline is recorded using thermal lens effect with optical parametric oscillator as the pump source. Studies show that the two-photon absorption spectrum observed corresponds to I Al -. I B2 transition of aniline.

Side illumination fluorescence emission characteristics from a dye doped polymer optical fiber under two-photon excitation.

Two-photon excited (TPE) side illumination fluorescence studies in a Rh6G-RhB dye mixture doped polymer optical fiber (POF) and the effect of energy transfer on the attenuation coefficient is reported. The dye doped POF is pumped sideways using 800 nm, 70 fs laser pulses from a Ti:sapphire laser, and the TPE fluorescence emission is collected from the end of the fiber for different propagation distances. The fluorescence intensity of RhB doped POF is enhanced in the presence of Rh6G as a result of energy transfer from Rh6G to RhB. Because of the reabsorption and reemission process in dye molecules, an effective energy transfer is observed from the shorter wavelength part of the fluorescence spectrum to the longer wavelength part as the propagation distance is increased in dye doped POF. An energy transfer coefficient is found to be higher at shorter propagation distances compared to longer distances. A TPE fluorescence signal is used to characterize the optical attenuation coefficient in dye doped POF. The attenuation coefficient decreases at longer propagation distances due to the reabsorption and reemission process taking place within the dye doped fiber as the propagation distance is increased.

Photoacoustic detection of two photon absorption in formaldehyde using pulsed dye laser

Absorption spectra of formaldehyde molecule in the gas phase have been recorded using photoacoustic (PA) technique with pulsed dye laser at various power levels. The spectral profiles at higher power levels are found to be different from that obtained at lower laser powers. Two photon absorption (TPA) is found to be responsible for the photoacoustic signal at higher laser power while the absorption at lower laser power level is attributed to one photon absorption (OPA) process. Probable assignments for the different transitions are given in this paper.

Observation of two-photon induced photoemission optogalvanic effect

Observation of laser induced two-photon photoemission optogalvanic (TPPOG) effect from tungsten electrode in a discharge cell using 564 nm radiation obtained from a pulsed dye laser is described. The magnitude of the POG signal is studied as a function of laser energy under various discharge parameters. Competition between one-photon and two-photon processes has been observed when nitrogen gas is used in the discharge cell.

Observation of two-photon absorption in rhodamine 6G using photoacoustic technique

Two-photon absorption in Rhodamine 6G using the second harmonic of a pulsed Q-switched Nd:YAG laser has been studied by photoacoustic technique. It is observed that there is a competition between one-photon and two-photon absorption processes. At lower concentration the two-photon process is predominant over the one-photon process.

Two and Three Photon Absorption in Rhodamine 6G Methanol Solutions Using Pulsed Thermal Lens Technique

Dual beam transient thermal lens studies were carried out in rhodamine 6G methanol solutions using 532 nm pulses from a frequency doubled Nd:YAG laser. Analysis of thermal lens signal shows the existence of different nonlinear processes like two photon absorption and three photon absorption phenomena along with one photon absorption. Concentration of the dye in the solution has been found to influence the occurrence of the different processes in a significant way.

Laser Induced Thermal Lens Effect in Rhodamine B — Signature of Resonant Two Photon Absorption

Measurement of thermal lensing signal as a function of laser power made in Rhodamine B solutions in methanol give clear evidence of two photon absorption process within certain concentration ranges when 488 nm Ar+ laser beam is used as the pump source. Only one photon process is found to occur when 514 nm and 476 nm beams are used as the pump.

Nd:Glass laser-induced damage to thin films, two-photon excited fluorescence and plasma studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out. The thesis is presented in seven chapters.

Nd:Glass Laser-Induced Damage To Thin Films, Two-Photon Excited Fluorescence And Plasma Studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out.