The infrared vibrational-rotational spectra of the deuterated triatomic hydrogen molecular ions, H₂D⁺, HD₂⁺, and D₃⁺ have been observed with the Doppler-tuned ion-beam laser spectroscopic method with collision detection. Triatomic hydrogen molecular ions are produced in a coaxial electron-impact ion source. Next, the ions are accelerated and formed into a beam of several keV energy, which is then intercepted at a small angle by a frequency-stabilized CO laser beam. The energy of the ion beam is adjusted to Doppler-shift an ion transition into resonance with a nearby laser line. On resonance, the laser light stimulates the transition to take place. If the resonating states differ in population, the laser-induced transition produces a net population transfer. The occurrence of population transfer is detected by monitoring the transmission of the ion beam through a gas target after laser interaction. The transmission through the target is dependent upon the ion beam population distribution and, therefore, the laser-induced transition can be detected by detecting the change of the transmission of the ion beam. A mass analyzer before the target gas facilitates the mass identification of the observed transitions. We have measured 45 D₃⁺ transition frequencies, 9 H₂D⁺ transition frequencies, and 31 HD₂⁺ transition frequencies, all between 1650 and 2000 cm⁻¹, to better than ±0.0005 cm⁻¹ or ±0.3 ppm. The identifications of the quantum numbers are still in progress. This study should greatly help the search of H₃⁺ and H₂D⁺ ions in interstellar medium.

No description available.

No description available.

No description available.

Gases at satisfactory pressures fluoresce in the presence of radio frequency radiation (6). Such fluorescent gases have been used to probe fields of radio frequency oscillation and their emission spectra have been recorded and studied. Ions with multiple charges also exist in these gases, (6). In 1941 Oliver (12) observed the fluorescence of an isobutane- isobutene gaseous mix flowing to a pump through a glass tube which was wrapped by a spiral antenna of a sevenmegacycle transmitter. A white deposit was noticed at a bend in the tubing on the pump side of the fluorescing section of the gas (12, p. 8). In 1957 Blacknall (3) studied the fluorescence and reaction products of propylene in the antenna region of sevenmega- cycle radiation, The oscillator employed by Blacknall was an ARC-5/T-22 military surplus transmitter of range 7.00 to 9.10 megacycles, which he operated at 7.00 megacycles. Blacknall observed a drop in pressure and the formation of a brown deposit in the region of the coil. Blacknall did not report an analysis of this product. In 1959 Armstrong (1) repeated Blacknall's experiments and modified Blacknall's apparatus into an improved design. He also performed an analysis on Blacknall's product. Blacknall used a vertical open-end mercurial manometer with which to measure pressure in his system and as a result introduced mercury vapor into his system. Armstrong tried to minimize the amount of mercury introduced by covering his manometric mercury with a layer of octyl sebacate, "octoil". Armstrong used a spiral-would antenna wrapped around his reaction vessel and reported the formation of spiral brown rings coincident with the copper wire of the antenna. There was a white product deposited in a spiral interlaced with the spiral of dark brown material. No definite identification was reported by Armstrong other than reporting, his solid material as isotactic polypropylene. Other work on electrodeless discharge of organic chemicals has been done in 1960 by Durward Smith and William Smith (13), in 1961 by Jimmie McCarty (10), and in 1963-64 by David Flinn (4).

Call number: LD2668 .T4 1957 K63 / Master of Science

OH-stretching spectra of various vapour phase species were recorded to investigate hydrogen bonding. The species studied include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, acetylacetone, hexafluoroacetylacetone and the complex formed in the heterogeneous mixture of methanol and trimethylamine. The spectra range from the infrared, near infrared to visible wavelengths. The main focus of this study is in the near infrared region, in which the OH-stretching overtones are dominant. The near infrared and visible spectrum of formic acid has been recorded to investigate coupling across bonds, specifically a resonance occurring between OH- and CH-stretching vibrations. The same resonance was also observed in the spectrum of 1,2-ethanediol. The spectra of deuterated isotopomers of formic acid and 1,2-ethanediol were recorded to experimentally verify the resonance. The inherently weak nature of the vibrational overtone transitions required sensitive spectroscopic techniques to observe the spectra. The spectra were recorded with conventional long path length absorption spectroscopy and intracavity laser photoacoustic spectroscopy. Anharmonic oscillator local mode calculations of the OH-stretching transitions were performed to simulate the observed spectra. These calculations require calculation of potential energy surfaces and dipole moment functions. Simulated spectra obtained with highly correlated ab initio methods and large basis sets have yielded the best agreement with observation.

Thesis (Ph. D.)--Texas Christian University, 2007. / Title from dissertation title page (viewed Dec. 10, 2007). Includes abstract. Includes bibliographical references.

New, rapid techniques to quantify the different pools of soil organic matter (SOM) are needed to improve our understanding of the dynamics and spatio-temporal variability of SOM in terrestrial ecosystems. In this study, total organic carbon (TOC) and oxidizable organic carbon (OCWB) fraction were calibrated and predicted by mid- and near-DRIFT spectroscopy in combination with partial least squares (PLS) regression method. PLS regression is a multivariate calibration method that can decompose spectral data (X) and soil property data (Y) into a new smaller set of latent variables and their scores that best describe all the variance in the data. Oxidizable organic carbon content was measured by a modified Walkley-Black method, and total organic carbon was measured by the carbon analyzer. The floodplain and Blackland Prairie soils in Texas were used for prediction of TOC and OCWB using mid- and near-DRIFT spectroscopy. Floodplain soil is mainly composed of quartz and kaolinite, whereas Blackland Prairie soils contain high concentrations of smectitic clays and low to high concentrations of carbonate minerals. The total organic carbon of 68 soil samples from two Texas sites varied between 0.19 and 4.36 wt.% C, and the oxidizable organic carbon of 26 samples from floodplain soils was in the range of 0.05 to 1.33 wt.% C. TOC and OCWB of soil were successfully calibrated and predicted by the PLS regression method using mid- and near-DRIFT spectroscopy. The correlation using mid-IR spectra for TOC (r = 0.96, RMSEV = 0.32 for calibration; r = 0.93, RMSEP = 0.44 for prediction) was about the same as the near-IR result (r = 0.95, RMSEV = 0.37; r = 0.93, RMSEP = 0.42). Therefore, we can also use mid-infrared region for quantification of total organic carbon in soils. The PLS1 regression model (r = 0.92) for prediction of OCWB using mid-IR spectra was more accurate than the PLS2 regression model (r = 0.90). PLS models showed better correlation with spectral data than the univariate least square regression method(r = 0.83) with TOC measured by the carbon analyzer. This study shows that the partial least squares (PLS1) method using mid-and near-IR spectra of neat soil samples can be used to predict both total organic carbon and oxidizable carbon fraction as a fast and routine quantitative method.

Thesis (MSc)--University of Stellenbosch, 2008. / Bibliography. Also available via the Internet.