This thesis project has involved a study of forbidden radiation: a phenomenon studied in the discipline of Atomic Spectroscopy. Specifically, the forbidden spectral line 6647 A of Hg II was examined. This line is of mixed multipolarity in that it is composed of magnetic-dipole and electric-quadrupole radiation. Emission of these two multipolarities gives rise to an interference effect which is quite useful in determining the degree to which each multipolarity contributes to this forbidden line.The results of the study carried out here agree with the theoretical predictions made for this line. They indicate that less than two percent electric-quadrupole radiation is present in the line. This study of the interference effect demonstrates the importance of obtaining both the transverse and longitudinal views of the line relative to the direction of the magnetic field. Both views, it is felt, are necessary for experimental verification of the line's structure.

The spark spectra of Tellurium have been photographed from the infrared to the ultraviolet (9040 Å to 340 Å) on a variety of spectrographs including a 3-metre normal, incidence vacuum spectrograph, a 2-metre grazing incidence vacuum spectrograph, a 21-ft, concave grating spectrograph, a Hilger Medium Quartz and a Hilger large automatic prism spectrograph. Two sources were used -1) a disruptive electrodeless discharge and 2) a condensed spark in helium, The "pole effect" exhibited by the spectral lines excited in the spark enabled us to assign each line to its appropriate ionic parent, either Te I, Te II, Te III, or Te IV. These excitation assignments were confirmed and extended by observations with the electrodeless discharge, which excited all the spectra including Te V and Te VI, by varying the tellurium pressure and the length of the external spark-gap. Out of 6000 lines appearing on our plates 3500 have never been observed earlier. The region 2200 Å - 1300 Å has been photographed systematically for the first time since Lacroute's work (1928). The whole of the observed spectral region has been photographed for the first time under uniform conditions of controlled excitation. These data have been used to confirm, revise and extend the analyses of Te III, Te IV, Te V and Te VI. In both Te III and Te IV the resonance lines have been indentified for the first time. The number of classified lines have been increased from 160 to 560 in Te III and from 25 to 230 in Te IV, while the number of the levels has been increased from 40 to 85 in Te III and from 14 to 56 in Te IV. The values of the ionization potentials have been revised to 29.04 Volts (Te III) and 37.41 Volts (Te IV). The hydrogenic levels in Te IV are fitted by a core polarization parameter A = 715 which involves a core dipole polarizability ∝= 41.1 x 10ˉ²⁸ cm³. The extensions in Te V and Te VI do not involve such basic additions. In Te V, the number of classified lines have been increased from 27 to 156 and in Te VI from 10 to 25. Twenty-four and five levels have been added to Te V and Te VI respectively. The revised values of the Ionization Potentials are 58.63 Volts and 70.90 Volts for Te V and Te VI respectively. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

The spectra of tin have been photographed in the region between 350Å and 9000Å using as sources an electrodeless discharge and a condensed spark in helium. Exposure were taken by using a 3 meter normal incidence vacuum grating spectrograph and a Hilger E-478 large interchangeable quartz and glass prism spectrograph. Among thirty four hundred and four lines which were measured, two hundred and thirty five lines were classified in the spectra Sn I and Sn II on the basis of square arrays constructed by using the energy levels from Mrs. Sitterly's "Atomic Energy Levels", Volume III (1957). Five hundred and eleven lines are herein classified in the spectra Sn III, Sn IV and Sn V. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

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Metastable, electronically excited atoms (²Dº , ²Pº ) of phosphorus, arsenic and antimony have been observed following the isothermal flash photolysis of Group VA hydrides and trihalides. Several mechanisms for the production of these atoms are discussed. The decay of the excited atoms was observed to be rapid due to reactions with the transients produced in the flash photolysis of the parent compounds. Flash photolysis of the Group VA hydrides and trichlorides has yielded new electronic absorption spectra of the AsH and AsH₂, SbH and SbH₂, PC1, AsC1, and SbC1 free-radicals. Vibrational analysis on some of these spectra have been carried out. In the isothermal flash photolysis of cyanogen with Group VA hydrides, it is proposed that the following reactions of the cyanogen radical occur rapidly: CN + AH₃ → AH₂ + HCN (1) CN + AH₂ → AH + HCN (2) CN + AH → ACN + H (A=N,P,As) (3) → HCN + A* (A=P,As, Sb) (4) (formula omitted) HACN (A=N,P) (5) where A, unless specified, is N, P, As or Sb and * denotes electronic excitation. Three of the new electronic absorption spectra observed are tentatively attributed to the PCN, HPCN and AsCN free-radicals produced in reactions (3) and (5). The assignment of the other spectra is discussed. Reactions of CN with NF, PC1 and AsC1, corresponding to (3), have also been shown to occur rapidly. The reactions of the cyanogen radical in the flash photolysis of cyanogen with nitrous oxide, oxygen, water, and methyl isocyanate have also been studied and discussed. / Science, Faculty of / Chemistry, Department of / Graduate

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Typescript. / Thesis (Ph. D.)--University of Hawaii, 1967. / Bibliography: leaves 243-254. / xv, 254 l illus., tables

Thesis (Ph. D.)--University of Wisconsin, 1966. / "Energy level and line tables for one-electron atomic spectra [by] J. D. Garcia and J. E. Mack. Reprinted from Journal of the Optical Society of America, vol. 55, no. 6, 654-685, June 1965"; Inserted between leaves 45-78. Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

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