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Czerwinski, Kenneth R.
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article
β-Technetium Dichloride: Solid-State Modulated Structure, Electronic Structure, and Physical Properties
Abstract
A second polymorph of technetium dichloride, β-TcCl<sub>2</sub>, has been synthesized from the reaction of Tc metal and chlorine in a sealed tube at 450 °C. The crystallographic structure and physical properties of β-TcCl<sub>2</sub> have been investigated. The structure of β-TcCl<sub>2</sub> consists of infinite chains of face sharing [Tc<sub>2</sub>Cl<sub>8</sub>] units; within a chain, the T<sub>c</sub>≡T<sub>c</sub> vectors of two adjacent [T<sub>c</sub><sub>2</sub>Cl<sub>8</sub>] units are ordered in the long-range where perpendicular and/or parallel arrangement of Tc≡Tc vectors yields a modulated structure. Resistivity and Seebeck measurements performed on a β-T<sub>c</sub>Cl<sub>2</sub> single crystal indicate the compound to be a p-type semiconductor while a magnetic susceptibility measurement shows technetium dichloride to be diamagnetic. A band gap of 0.12(2) eV was determined by reflectance spectroscopy measurements. Theoretical calculations at the density functional level were utilized for the investigation of other possible stable forms of T<sub>c</sub>Cl<sub>2</sub>.