Some recent advances in high temperature photoelectron spectroscopy
This thesis deals with the study of a number of atoms and small molecules by high temperature photoelectron spectroscopy. The experimental techniques used to study these species in the vapour phase are described in detail in Chapter Two while the theoretical methods used to assign the spectra are outlined in Chapter Three. The work described shows that the experimental p.e. spectra of transition metals can be a valuable precursor to the study of transition metal oxides in the gas-phase. The Hel p.e. spectra of iron, cobalt and nickel are described in Chapter Six. These studies mean that all the first-row transition metals have now been studied with u.v.p.e.s. in the vapour phase and comparison of the HeIơ4s:ơ3d photoionisation cross-section ratiosis given in Chapter Six. The experimental spectra for iron, cobalt and nickel as well as results previously obtained for other first-row transition metals are used to monitor the vapour above a transition metal alloy as a function of temperature. The results of this study are given in Chapter Five. The HeI photoelectron spectra of CrO and VO are presented in Chapter Six and these are assigned with the aid of ab initio ASCF configuration interaction calculations (Chapter Four). Ab initio ASCF CI calculations are also used in the assignment of the photoelectron spectrum of AlF. This work is described in Chapter Seven where it is shown that an ionic rather than a covalent model is qualitatively more appropriate to interpret the spectra obtained.