The many phases of CaC{sub 2}

Polymorphic CaC{sub 2} was prepared by reacting mixtures of CaH{sub 2} and graphite with molar ratios between 1:1.8 and 1:2.2 at temperatures between 700 and 1400 °C under dynamic vacuum. These conditions provided a well controlled, homogeneous, chemical environment and afforded products with high purity. The products, which were characterized by powder X-ray diffraction, solid state NMR and Raman spectroscopy, represented mixtures of the three known polymorphs, tetragonal CaC{sub 2}-I and monoclinic CaC{sub 2}-II and -III. Their proportion is dependent on the nominal C/CaH{sub 2} ratio of the reaction mixture and temperature. Reactions with excess carbon produced a mixture virtually free from CaC{sub 2}-I, whereas high temperatures (above 1100 °C) and C-deficiency favored the formation of CaC{sub 2}-I. From first principles calculations it is shown that CaC{sub 2}-I is dynamically unstable within the harmonic approximation. This indicates that existing CaC{sub 2}-I is structurally/dynamically disordered and may possibly even occur as slightly carbon-deficient phase CaC{sub 2-δ}. It is proposed that monoclinic II is the ground state of CaC{sub 2} and polymorph III is stable at temperatures above 200 °C. Tetragonal I represents a metastable, heterogeneous, phase of CaC{sub 2}. It is argued that a complete understanding of the occurrence of three room temperature modifications of CaC{sub 2} will require a detailed characterization of compositional and structural heterogeneities within the high temperature form CaC{sub 2}-IV, which is stable above 450 °C. The effect of high pressure on the stability of the monoclinic forms of CaC{sub 2} was studied in a diamond anvil cell using Raman spectroscopy. CaC{sub 2}-II and -III transform into tetragonal CaC{sub 2}-I at about 4 and 1GPa, respectively. - Graphical abstract: The famous tetragonal form of CaC{sub 2}, CaC{sub 2}-I, is dynamically unstable. Why does it exist? Display Omitted - Highlights: • Critical review of complex polymorphism of the commodity chemical CaC{sub 2}. • Tetragonal CaC{sub 2}-I is identified as dynamical instable and its existence attributed to disorder. • With pressure monoclinic CaC{sub 2}-II and –III transform into tetragonal CaC{sub 2}-I. • The high temperature form CaC{sub 2}-IV is assigned a key role for understanding the polymorphism of CaC{sub 2}.