Copernicium: A Relativistic Noble Liquid

• Published in: Angewandte Chemie International Edition Vol. 58; no. 50; pp. 17964 - 17968
• Main Authors: Mewes, Jan‐Michael, Smits, Odile R., Kresse, Georg, Schwerdtfeger, Peter
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 09.12.2019; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: aggregate states; Boiling points; copernicium; free-energy calculations; Heavy metals; melting point; Mercury; Mercury (metal); Organic chemistry; Physicochemical properties; Relativism; Relativistic effects; superheavy elements; copernicium; superheavy elements; free-energy calculations; melting point; aggregate states
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201906966

The chemical nature and aggregate state of superheavy copernicium (Cn) have been subject of speculation for many years. While strong relativistic effects render Cn chemically inert, which led Pitzer to suggest a noble‐gas‐like behavior in 1975, Eichler and co‐workers in 2008 reported substantial interactions with a gold surface in atom‐at‐a‐time experiments, suggesting a metallic character and a solid aggregate state. Herein, we explore the physicochemical properties of Cn by means of first‐principles free‐energy calculations, which confirm Pitzer's original hypothesis: With predicted melting and boiling points of 283±11 K and 340±10 K, Cn is indeed a volatile liquid and exhibits a density very similar to that of mercury. However, in stark contrast to mercury and the lighter Group 12 metals, we find bulk Cn to be bound by dispersion and to exhibit a large band gap of 6.4 eV, which is consistent with a noble‐gas‐like character. This non‐group‐conforming behavior is eventually traced back to strong scalar‐relativistic effects, and in the non‐relativistic limit, Cn appears as a common Group 12 metal. The physicochemical properties of copernicium (Cn) were explored by means of first‐principles free‐energy calculations. The resulting melting and boiling points of 283±11 K and 340±10 K classify Cn as a volatile liquid, for which a density very similar to that of mercury is calculated. However, in contrast to metallic mercury, bulk Cn exhibits a large band gap of 6.4 eV and is dominated by dispersion interactions, which is consistent with a noble‐gas‐like character.