Titanium Dioxide has been a material of interest for almost fifty years due to its ability to photocatalyze chemical reactions on its surface under UV excitation. This thesis discusses the properties of electrons in the conduction band of TiO₂, which are probed by a variety of new experimental techniques as well as novel combinations of techniques. These measurements give insight into the electronic and photocatalytic properties of TiO₂, as well as characterizing a number of new excitations that have not been detected until now. The discovery of a transition from an occupied Ti-3d defect band of t_2g symmetry to an unoccupied e_g symmetry d band (d-d transitions) in TiO₂ gives a better understanding of the electronic structure in the surface region as well as providing a new method for probing the distribution of defect carriers in the bulk and surface. Additionally this newly discovered transition allowed for the identification and characterization of the polaron character of the initial state in photoemission process. A polaron state has been predicted by the theory, but experimental verification has been hard to achieve by spectroscopic means. Finally the interactions of molecules including CO₂, CH₃OH, and O₂ with the defect states was characterized by observing the effect of molecular adsorption on the d-d transitions. By varying the temperature, surface preparation and coverage of the adsorbates, the electron dynamics and interactions of these molecules were studied and produced an increased understanding of the importance of molecular interactions in regards to photoactivity of the surface. This work advances the general knowledge of TiO₂ and gives a solid framework for determining the complex electronic interactions that define its photocatalytic activity.