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Kinetics and dynamics measured using IntraCavity Laser Absorption Spectroscopy

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dc.contributor.advisor Jeffrey I. Steinfeld. en_US Witonsky, Scott Kenneth, 1975- en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US 2005-03-22T20:48:27Z 2005-03-22T20:48:27Z 2002 en_US 2002 en_US
dc.description Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2002. en_US
dc.description Vita. en_US
dc.description Includes bibliographical references (p. 133-138). en_US
dc.description.abstract IntraCavity Laser Absorption Spectroscopy (ICLAS) is a high-resolution, high sensitivity spectroscopic method capable of measuring line positions, linewidths, lineshapes, and absolute line intensities with a sensitivity that far exceeds that of a traditional multiple pass absorption cell or Fourier Transform spectrometer. From the fundamental knowledge obtained through these measurements, information about the underlying spectroscopy, dynamics, and kinetics of the species interrogated can be derived. The construction of an ICLA Spectrometer will be detailed, and the measurements utilizing ICLAS will be discussed, as well as the theory of operation and modifications of the experimental apparatus. Results include: i) Line intensities and collision-broadening coefficients of the A band of oxygen and previously unobserved, high J, rotational transitions of the A band, hot-band transitions, and transitions of isotopically substituted species. ii) High-resolution (0.013 cm-1) spectra of the second overtone of the OH stretch of trans-nitrous acid recorded between 10,230 and 10,350 cm-1. The spectra were analyzed to yield a complete set of rotational parameters and an absolute band intensity, and two groups of anharmonic perturbations were observed and analyzed. These findings are discussed in the context of the contribution of overtone-mediated processes to OH radical production in the lower atmosphere. en_US
dc.description.abstract (cont.) iii) The implementation of Correlated Double Sampling (CDS) for time-resolved studies of CN fragments generated by the excimer laser photolysis of acrylonitrile. iv) The extension of ICLAS to study the kinetics of a test system. Nitrosyl hydride, HNO, was reacted with oxygen in a flow cell, and the subsequent chemistry was monitored using an electronic transition of HNO. Analysis of the rate equations and time integrated measured signal yielded a preliminary value for the rate constant of the reaction, HNO + 02 [right arrow] products. en_US
dc.description.statementofresponsibility by Scott Kenneth Witonsky. en_US
dc.format.extent 139 p. en_US
dc.format.extent 10321376 bytes
dc.format.extent 10321130 bytes
dc.format.mimetype application/pdf
dc.format.mimetype application/pdf
dc.language.iso eng en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. en_US
dc.subject Chemistry. en_US
dc.title Kinetics and dynamics measured using IntraCavity Laser Absorption Spectroscopy en_US
dc.title.alternative Kinetics and dynamics measured using ICLAS en_US
dc.type Thesis en_US Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 51006858 en_US

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