Pathways for Photolysis of Titanium Tetrachloride

The primary photodissociation pathways of titanium tetrachloride following excitation at 266 nm have been studied with the fluorescence method in the static gas cell. A great many fluorescence lines of titanium atoms are observed in photolysis of TiCl₄. The excitation leading to a charge transfer transition from chlorine to titanium 3d orbital results mainly in photodissociation of TiCl₄ into Ti^*. The possibility of photoionization of TiCl₄ to (TiCl₄)⁺ is very small, which is discussed in detail in the paper based on the experimental results and the properties of energetic structures of TiCl₄. A general deseription of photofragmentation of molecules is presented.