Computational quantum chemistry has made fantastic strides in the last 30 years. Often deep insight into all sorts of questions regarding reactions and structures of molecules has become possible. But sometimes the simplest of questions can prove incredibly difficult to answer. One such is how accurately can the boiling point of water be predicted from first principles? Or its melting point?
AbstractThe 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.