Three gas phase alkaline earth molecules were analyzed using dye laser spectroscopy. The A¹Σ⁺ - X¹Σ⁺ transition of gas phase SrS was studied with high resolution techniques. The 0-0, 0-1, 1-1, 2-1, 3-0, 3-2, 4-1, 5-1, and 5-2 bands were rotationally analyzed and spectroscopic constants were determined. The A¹Σ⁺ state was extensively perturbed. Ground state (X¹Σ⁺) constants derived from the analysis of the nine vibrational levels include: ωₑ = 388.2643 cm⁻¹, Bₑ = 0.1208034(33) cm⁻¹, and rₑ = 2.439687(14) Å. Excited state (A¹Σ⁺) constants determined include: Tₑ = 13932.7068(10) cm⁻¹, ωₑ = 339.1454(20) cm⁻¹, Bₑ = 0.1139895(38) cm⁻¹, and rₑ = 2.511601(17) Å. The spectra of calcium and strontium borohydrides were observed using low resolution laser spectroscopy. The spectra were assigned to the òA₁ - Ẋ²A₁ and Ḃ²E - Ẋ²A₁ transitions of CaBH₄ and SrBH₄. The vibrational frequencies of the metal-ligand stretch determined for CaBH₄ were 457 cm⁻¹ (Ẋ²A₁), 473 cm⁻¹ (Ā²A₁), and 465 cm⁻¹ (Ḃ²E). The corresponding SrBH4 frequencies were 399 cm⁻¹, 420 cm⁻¹, and 421 cm⁻¹.

This thesis is divided into two parts; Part I consisting of the theory and Part II the experimental work. Part I is divided into three sections; in Section 1 a summary is given of collision processes and how they have been used to explain various experimental results; this is followed in Section 2 by the author's interpretation of some previous experimental observations; a summary of the wave mechanical theory of collisions is given in Section 3. Part II consists of four sections; In Section 1an outline is given of the various ways of exciting spectra and this is followed by a description of the apparatus used by the author in Section 2; the results of the experiments with hydrogen and oxygen are given in Section 3, and the theoretical interpretation of these; the last Section deals with the experiments carried out with hydrogen and helium, and the facts which may be inferred from these experimental results.

The products from a gaseous r.f. electric discharge in ammonia have been studied using electron spin resonance spectroscopy. A paramagnetic species from the discharge was detected and the results were consistent with it being the imine (NH) free radical. The E.S.R. Spectrum fitted the theoretical treatment and was similar to that observed for NH in a frozen matrix. No other radicals could be detected in the discharge except for the atomic species. The low pressure gas phase E.S.R. spectrum of (formula omitted) was also studied. The results showed that at low pressures the spectrum becomes exceedingly complex. A partial assignment of lines was made from the results of a simplified treatment of the theory. The work served a further purpose in developing experimental techniques for the study of unstable free radical species in the gas phase. / Science, Faculty of / Chemistry, Department of / Graduate

Call number: LD2668 .T4 1984 L56 / Master of Science

Absolute K-shell x-ray cross sections and Auger-electron cross sections are measured for carbon for 0.6 to 2.0 MeV proton incident on CH₄, n-C₄H₁₀ (n-Butane), i-C₄H₁₀ (isobutane), C₆H₆ (Benzene), C₂H₂ (Acetylene), CO and CO₂. Carbon K-shell fluorescence yields are calculated from the measurements of x-ray and Auger-electron cross sections. X-ray cross sections are measured using a variable geometry end window proportional counter. An alternate method is described for the measurement of the transmission of the proportional counter window. Auger electrons are detected by using a constant transmission energy Π/4 parallel pi ate electrostatic analyzer. Absolute carbon K-shell x-ray cross sections for CH₄ are compared to the known results of Khan et al. (1965). Auger-electron cross sections for proton impact on CH₄ are compared to the known experimental values of RΦdbro et al. (1979), and to the theoretical predictions of the first Born and ECPSSR. The data is in good agreement with both the first Born and ECPSSR, and within our experimental uncertainties with the measurements of RΦdbro et al. The x-ray cross sections, Auger-electron cross sections and fluorescence yields are plotted as a function of the Pauling charge, and show significant variations. These changes in the x-ray cross sections are compared to a model based on the number of electrons present in the 2s and 2p sub shells of these carbon based molecules. The changes in the Auger-electron cross sections are compared to the calculations of Matthews and Hopkins. The variation in the fluorescence yield is explained on the basis of the multiconfiguration Dirac-Fock model.