Title

Photoelectron Studies Of Ligand Field Effects, Vibrational Broadening And Shakeup

Date of Award

1982

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Abstract

High resolution HeI and HeII spectra have been obtained of the zinc and cadmium dihalides and thallium monohalides (excluding fluorides). Spin-orbit splitting in the valence bands has been clearly resolved for the first time and second order effects have been interpreted quantitatively.;The outermost metal core d-levels exhibit fine structure splitting which is shown to be a combination of spin-orbit coupling, ligand field splitting and to a small extent, bonding effects. This splitting is proportional to the asymmetric ligand field potential as defined by the C(DEGREES)(,2) parameter. The magnitude of C(DEGREES)(,2) is shown to be a combination of point charge and valence contributions.;Both an experimental and theoretical study of cross section variations in the valence bands of the zinc and cadmium halides and outer core d-levels of zinc halides has been carried out. Our studies have demonstrated conclusively that individual components of a particular orbital differing only in (LAMDA), can exhibit marked differences in relative cross sections. This is especially true to close to the ionization threshold where shape resonance effects play a significant role.;Vibrational broadening in fluorine 1s core level spectra has been interpreted witin an equivalent cores formalism. Using this model, it is possible to correlate the flourine 1s full width at half maximum with the equivalent cores dissociation energy.;Both experimental and theoretical shakeup studies have been carried out on the rare gases and rare gas fluorides. An atomic model utilizing the shakeup spectra of Kr and Xe to assign the more complex fluoride spectra has been developed. Shakeup energies and intensities have also been calculated using an X(alpha)-SW calculation and excellent agreement with experiment is observed.

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