High-temperature photoelectron spectroscopy of alkali metaborates, alkali tetrachloroaluminates, alkali tetrafluoroaluminates, and ammonium tetrachloroaluminate
Date Issued
June 1, 1979
Author(s)
Lassiter, Thomas Warren.
Advisor(s)
G. K. Schweitzer
Abstract
The high temperature Hel photoelectron spectra of the gas phase molecules K+BO2-, Rb+BO 2-, Cs +BO2-, K+A1C14-,Rs +A1C14-, Cs+A1C14-, NH4 A1C14-,K+A1F 4-, and Cs+A1F 4- have been obtained. The vapors were produced by resistance heating a tantalum-strip-wound boron nitride oven (K+BO2-, Rb+BO 2- , and Cs +BO2-) or a tantalum-strip-wound platinumlined quartz sample oven (K+A1C14-, Rb +A1C14-, Cs +A1C14-, NH +A1C14-, K +A1F 4- , and Cs +A1F 4- ) containing the solid compounds. Both ovens were coated with a high temperature ceramic cement, Analysis of the ejected electrons was carried out using a modified truncated cylindricalmirror-electron spectrometer. The identities of the vapor phase enti ties above the corresponding solids were correlated with data from the techniques of electron diffraction, mass spectrometry, matrix isolation and vapor infrared spectroscopies, The ionization energies were assigned molecular orbital origins through the use of molecular orbital calculations, and comparisons with X-ray, Hel, and Hell photoelectron data for the solids, and for analogous compounds.
A high temperature structural model called polytopic bonding was thought to be applicable to these high temperature species because all the experimental photoelectron spectra of the same anion were very similar and all the experimental data were correlated with theoretical calculations for the corresponding free anion, However, the observed band breadths were considerably greater than the splits which were expected on the basis of theoretical calculations for various structural parameter changes. Therefore, no judgment could be made concerning the possible polytopicity of these compounds at high temperature.
Degree
Doctor of Philosophy
Major
Chemistry
File(s)![Thumbnail Image]()
Name
Thesis79b.L388.pdf
Size
5.73 MB
Format
Adobe PDF
Checksum (MD5)
cd4d3c5a31be84ee3fb449dd51f5de89