Single-crystal growth and electronic structure of Tl3PbCl5, a prospective nonlinear optical material

High-quality Tl₃PbCl₅ single crystal has been grown employing the Bridgman-Stockbarger technique in a two-zone furnace. For the Tl₃PbCl₅ single crystal, X-ray photoelectron spectra for mechanically cleaned surface have been measured. To elucidate the electronic structure of Tl₃PbCl₅, the Korringa-Kohn-Rostoker method within coherent potential approximation (KKR-CPA) has been used to calculate total and partial densities of states of the constituent atoms. The KKR-CPA data reveal that the valence band of Tl₃PbCl₅ is dominated by contributions of the Cl 3p-like states. These states contribute mainly into the top and the central portion of the valence band with also significant contributions throughout the whole valence-band region of Tl₃PbCl₅. Furthermore, the Tl 6s-like states dominate at the bottom of the valence band of Tl₃PbCl₅, while the bottom of the conduction band is dominated by contributions of the Pb 6p*-like states.