Date of Award
1987
Degree Type
Dissertation
Degree Name
Doctor of Philosophy
Abstract
High resolution He {dollar}{lcub}\rm I{rcub}\alpha{dollar} and He {dollar}{lcub}\rm II{rcub}\alpha{dollar} photoelectron spectra of the gas phase indium (I) and indium (III) halides have been obtained. The In 4d spectra of the indium (I) halides exhibited fine structure splitting due to the combined effects of spin-orbit coupling and ligand field splitting. The absence of any resolvable ligand field splitting in the In 4d spectra of indium (III) iodide and indium (III) bromide indicated that these compounds were dimeric in the gas phase. MS-X{dollar}\alpha{dollar} calculations were performed on both the indium (I) and indium (III) halides.;The inclusion of relativistic corrections to MS-X{dollar}\alpha{dollar} calculations performed on the lead (II) halides improved the agreement between theoretical and experimental valence band binding energies.;In a high resolution He {dollar}{lcub}\rm I{rcub}\alpha{dollar} photoelectron spectrum obtained for {dollar}{lcub}\rm MoWCl\sb4 (PMe\sb3)\sb4{rcub},{dollar} three valence band peaks were resolved at low binding energy and were assigned to the {dollar}\delta{dollar}, {dollar}\pi{dollar} and {dollar}\sigma{dollar} metal-metal bonding orbitals.;Using monochromatized synchrotron radiation, gas phase photoelectron spectra of the valence and Hg 5d levels of {dollar}{lcub}\rm Hg(CH\sb3)\sb2{rcub},{dollar} the valence levels of {dollar}{lcub}\rm Si(CH\sb3)\sb4{rcub}{dollar} and the valence and Sn 4d levels of {dollar}{lcub}\rm Sn(CH\sb3)\sb4{rcub}{dollar} were obtained as a function of photon energy. Valence level branching ratios were obtained between 21 and 70 eV photon energy. Theoretical branching ratios and partial cross sections were obtained from MS-X{dollar}\alpha{dollar} calculations and compared with experimental results. Resonances were predicted and observed in the {dollar}3{lcub}\rm a{rcub}\sb1\sp\prime{dollar} orbital of {dollar}{lcub}\rm Hg(CH\sb3)\sb2{rcub}{dollar} and in the {dollar}3{lcub}\rm t{rcub}\sb2{dollar} and {dollar}2{lcub}\rm a{rcub}\sb1{dollar} orbitals of {dollar}{lcub}\rm Si(CH\sb3)\sb4{rcub}{dollar} and {dollar}{lcub}\rm Sn(CH\sb3)\sb4{rcub}.{dollar} Intershell correlations were observed in the experimental branching ratio behaviour of the {dollar}3{lcub}\rm a{rcub}\sb1\sp\prime{dollar} orbital of {dollar}{lcub}\rm Hg(CH\sb3)\sb2{rcub}{dollar} and the {dollar}3{lcub}\rm t{rcub}\sb2{dollar} orbital of {dollar}{lcub}\rm Sn(CH\sb3)\sb4.{rcub}{dollar};The Hg {dollar}5{lcub}\rm d{rcub}\sb{lcub}5/2{rcub}{dollar}:{dollar}5{lcub}\rm d{rcub}\sb{lcub}3/2{rcub}{dollar} ratio of {dollar}{lcub}\rm Hg(CH\sb3)\sb2{rcub}{dollar} and the Sn {dollar}4{lcub}\rm d{rcub}\sb{lcub}5/2{rcub}{dollar}:{dollar}4{lcub}\rm d{rcub}\sb{lcub}3/2{rcub}{dollar} ratio of {dollar}{lcub}\rm Sn(CH\sb3)\sb4{rcub}{dollar} were both found to deviate significantly from the statistical value of 1.5.
Recommended Citation
Bice, Jo-ann Edith, "Gas Phase Photoelectron Studies Using Helium(i), Helium(ii) And Synchrotron Radiation" (1987). Digitized Theses. 1587.
https://ir.lib.uwo.ca/digitizedtheses/1587