41 |
Further development of NICE-OHMS : – an ultra-sensitive frequency-modulated cavity-enhanced laser-based spectroscopic technique for detection of molecules in gas phaseEhlers, Patrick January 2014 (has links)
Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy, NICE-OHMS, is a laser-based spectroscopic detection technique that comprises the concepts of frequency modulation (FM, for reduction of 1/f-noise by detecting the signal at a high frequency) and cavity enhancement (CE, for a prolongation of the optical path length) in a unique way. Properly designed, this gives the technique an intrinsic immunity against the frequency-to-noise conversion that limits many other types of CE techniques. All this gives it an exceptionally high sensitivity for detection of molecular species. Although originally developed for frequency standard purposes in the late 1990s, soon thereafter development of the technique towards molecular spectroscopy and trace gas detection was initiated. This thesis focuses on the further development of Doppler- broadened NICE-OHMS towards an ultra-sensitive detection technique. A number of concepts have been addressed. A few of these are: i) The detection sensitivity of fiber-laser-based NICE- OHMS has been improved to the 10−12 cm−1 range, which for detection of C2H2 corresponds to a few ppt (parts-per-trillion, 1:1012) in gas phase, by improving the locking of the laser to a cavity mode by use of an acousto-optic modulator. ii) It is shown that the system can be realized with a more compact footprint by implementation of a fiber-optic circulator. iii) A systematic and thorough investigation of the experimental conditions that provide maximum signals, referred to as the optimum conditions, e.g. modulation and demodulation conditions and cavity length, has been performed. As a part of this, an expression for the NICE-OHMS line shape beyond the conventional triplet formalism has been proposed and verified. iv) To widen the applicability of NICE-OHMS for detection of pressure broadened signals, also a setup based upon a distributed-feedback (DFB) laser has been realized. v) In this regime, the Voigt profile cannot model signals with the accuracy that is needed for a proper assessment of analyte concentrations. Therefore, the thesis demonstrates the first implementations of line profiles encompassing Dicke narrowing and speed-dependent effects to NICE-OHMS. While such profiles are well-known for absorption, there were no expressions available for their dispersion counterparts. Such expressions have been derived and validated by accompanying experiments. vi) The applicability of the technique for elemental detection, then referred to as NICE-AAS, has been prophesied. / Brusimmun kavitetsförstärkt optisk-heterodyndetekterad molekylärspektroskopi (NICE-OHMS) är en laser-baserad spektroskopisk teknik som förenar frekvensmodulation (för reducring av 1/f-brus genom detektion vid en hög frekvens) och kavitetsförstärkning (KF, för en förlängning av den optiska väglangden) på ett unikt sätt. Korrekt realiserad uppvisar tekniken en inneboende immunitet mot omvandling av frekvensbrus till intensitetsbrus som många andra KF-tekniker är begränsade av. Allt detta ger tekniken en exceptionellt hög känslighet för molekyldetektion. Ursprungligen utvecklad för frekvensstandardändamål i slutet av 1990, har den sedan dess utvecklats för molekylspektroskopi och spårgasdetektering. Denna avhandling fokuserar på vidareutvecklingen av NICE-OHMS mot en tillämpbar, ultrakänslig detektionsteknik. Ett antal koncept har adresserats. Några av dessa är: i) Detektionskänsligheten hos fiberlaserbaserad NICE-OHMS har förbättrats till 10-12 cm-1 området, vilket för detektion av C2H2 i gasfas motsvarar några få ppt (parts per biljon, 1:1012), genom att förbättra låsningen av lasern till en kavitetsmod med hjälp av en akustooptisk modulator. ii) Det har demonstrerats att NICE-OHMS kan realiseras mer kompakt med hjälp av en fiber-kopplad optisk cirkulator. iii) En systematisk och grundlig utredning av de experimentella förhållanden som ger maximala signaler, betecknade de optimala förhållanden, t.ex. modulering och demodulering och kavitetslängden, har utförts. Som ett led i detta har ett uttryck för NICE-OHMS linjeform bortom den konventionella triplett formalismen föreslagits och verifierats. iv) För att bredda tillämpbarheten av NICE-OHMS för detektering av tryckbreddade signaler har även en instrumentering baserad på en distribuerad-återkopplad (eng. distributed feedback, DFB) laser realiserats. v) I detta område kan inte Voigt profilen modellera signalen med den noggrannhet som krävs för en korrekt bedömning av analytkoncentrationer. Därför visar avhandlingen de första implementeringarna i NICE-OHMS av linjeprofiler som inkluderar Dicke avsmalning (eng. Dicke narrowing) och hastighetsberoende effekter (eng. speed-dependent effects). Emedan sådana profiler är välkända för absorption, fanns det inga uttryck för deras dispersiva motparter. Sådana uttryck har därför härletts och validerats av medföljande experiment. vi) Tillämpbarheten av tekniken för detektion av atomer, NICE-AAS, har diskuterats och förutspåtts. / <p>Ytterligare forskningsfinansiär: Kempestiftelserna</p>
|
42 |
Quantum chaos of the NO2 molecule in high magnetic fieldsNygård, Jesper. January 1900 (has links) (PDF)
Thesis (M.S.)--Københavns universitet, 1996. / Title from title screen (viewed on July 9, 2008). Title from document title page. Includes bibliographical references. Available in PDF format via the World Wide Web.
|
43 |
Near-ir tunable diode laser absorption spectroscopy of gaseous pollutants /Chan, Kit-ying, Anna. January 1998 (has links)
Thesis (M. Phil.)--University of Hong Kong, 1998. / Includes bibliographical references.
|
44 |
Collisional depolarization of the atomic Cs 6s<sup>2</sup>S<sub>1/2</sub>-10s<sup>2</sup>S<sub>3/2</sub>,9d<sup>2</sup>D<sub>5/2</sub> transition with argon buffer gasSeda, Kin. January 2005 (has links)
Thesis (Master of Science)--Miami University, Dept. of Physics, 2005. / Title from first page of PDF document. Document formatted into pages; contains [1], ???, ??? p. : ill. Includes bibliographical references (p. Xx-Xx).
|
45 |
Low temperature helium pressure broadening of HCNRonningen, Theodore J., January 2005 (has links)
Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xiv, 218 p.; also includes graphics (some col.) Includes bibliographical references (p. 208-218). Available online via OhioLINK's ETD Center
|
46 |
Conformational stability from temperature-dependent infrared spectra of noble gas solutions, normal coordinate analyses, adjusted r₀ structural parameters and barrier to internal rotation of some substituted amine, hydrazine and three-membered ring compoundsZheng, Chao, Durig, James R. January 2006 (has links)
Thesis (Ph. D.)--Dept. of Chemistry and Dept. of Physics. University of Missouri--Kansas City, 2006. / "A dissertation in chemistry and physics." Advisor: James R. Durig. Typescript. Vita. Description based on contents viewed Jan. 29, 2007; title from "catalog record" of the print edition. Includes bibliographical references (leaves 447-460). Online version of the print edition.
|
47 |
Characterization and applications of surface enhanced vibrational spectroscopy /Heaps, David Allyn. January 1900 (has links)
Thesis (Ph. D.)--University of Idaho, 2005. / Also available online in PDF format Abstract. "October 2005." Includes bibliographical references.
|
48 |
Dosage des polluants NO et CO par imagerie de fluorescence induite par laser dans les écoulements réactifs / Probing of NO and CO pollutants in reactive flowfields by planar laser-induced fluorescenceGautier, Pierre 19 December 2017 (has links)
La thèse consiste à développer une technique d'imagerie quantitative de concentration de polluants dans les écoulements réactifs. Il s'agit d'une part de développer l'imagerie de fluorescence sur NO. Un modèle de fluorescence à n niveaux a été développé pour calculer l'évolution de la fluorescence avec la température, concentration des espèces et pression. Ce modèle a été validé avec des mesures de fluorescence et d'absorption obtenues dans une cellule optique fonctionnant jusqu'à 800 K et 20 bar puis dans un brûleur laminaire haute-pression. De ce modèle a été définie une stratégie permettant la mesure de la distribution instantanée de NO dans une flamme stratifiée. Une étude similaire pour détecter CO a été ensuite initiée. Des mesures de fluorescence à deux photons ont été obtenues dans la cellule et dans une flamme plate atmosphérique. Les résultats montrent que cet outil est opérationnel, répondant à un besoin pour l'amélioration des performances des systèmes de propulsion. / This PhD work is to develop a quantitative imaging technique for measurements of the concentration of pollutants in reactive flows. On one hand, the concern was to develop the NO fluorescence imaging technique. For this purpose, an n-level fluorescence model was first developed to calculate the behavior of fluorescence signals with temperature, species concentration, and pressure. Then this model was validated with fluorescence and absorption measurements acquired in an optical cell up to 800 K and to 20 bar and in a high-pressure laminar burner. From this model, a strategy used to measure the instantaneous NO distribution in a stratified flame was defined. Then, a similar study to detect CO with fluorescence was then investigated. Two-photon fluorescence measurements were performed in the optical cell and in a flame. The results make clear that the spectroscopic diagnostic becomes operational with the need to improve the performances of propulsion systems.
|
49 |
Novel Improvements On The Analytical Chemistry Of Polycyclic Aromatic Hydrocarbons And Their MetabolitesHuiyong, Wang 01 January 2010 (has links)
Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation preconcentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatographymass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identification is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to "unfamiliar" samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen "priority pollutants" (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector’s response range, the sample must be diluted and the process repeated. These are important considerations iv when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component – which we have named solid-phase nano-extraction (SPNE) - deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC1 and Laser-Excited TimeResolved Shpol’skii Spectroscopy (LETRSS).2 The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC3 and In-Capillary SPNE-CE.4 The second original component of this dissertation describes the application of Shpol’skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and v sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol’skii spectroscopy a leading technique in environmental analysis.5 Unfortunately, the requirement of a specific guest-host combination - typically a non-polar PAH dissolved in an n-alkane - has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzo[a]pyrene metabolites in alcohol matrixes.6
|
50 |
Spectroscopy Studies of Free Radicals and Ions Containing Large Amplitude MotionsHuang, Meng 02 August 2018 (has links)
No description available.
|
Page generated in 0.0717 seconds