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This thesis is concerned with the development and application of high resolution threshold photodetachment spectroscopy of negative ions. Chapter I deals with the principles of our photodetachment technique, and in chapter II a detailed description of the apparatus is presented. The threshold photodetachment spectra of I{sup {minus}}, and SH{sup {minus}}, presented in the last sections of chapter II, indicated that a resolution of 3 cm{sup {minus}1} can be achieved using our technique. In chapter III the threshold photodetachment spectroscopy study of the transition state region of I + HI and I + Di reactions is discussed. Our technique probes the transition state region directly, and the results of our study are the first unambiguous observations of reactive resonances in a chemical reaction. Chapters IV, V and VI are concerned with the spectroscopy of small silicon and carbon clusters. From our spectra we were able to assign electronic state energies and vibrational frequencies for the low lying electronics states of Si{sub n} (n=2,3,4), C{sub 5} and their corresponding anions.

Threshold photodetachment spectroscopy of negative ions