A suitable representative structure is a three-dimensional network of corner-sharing CO tetrahedra, with C–O single bonds. Each carbon is four-coordinate; every bridging oxygen is bonded to two carbons. Sharing four oxygens between two tetrahedra gives oxygens per carbon, so the network retains empirical formula CO without containing separate O=C=O molecules.
High pressure favours a compact, highly coordinated network through its smaller molar volume: at fixed temperature, increasing pressure changes relative Gibbs energies according to . Heating helps overcome the large reconstructive barrier to breaking and redistributing molecular pi bonding and establishing an extended single-bond network. It should not be argued that high temperature by itself favours the lower-entropy network. Nor is merely freezing molecular CO sufficient: dry ice remains a molecular solid.
The sketch shows connectivity and local tetrahedral coordination, not a unique predicted crystal structure. Real amorphous carbonia need not have perfect periodic order or exclusively one coordination environment. The original carbonia experiments combined high-pressure preparation with infrared, Raman and diffraction evidence for loss of molecular character and formation of an amorphous network.[ref]
Figure 1.
Original representative corner-sharing tetrahedral CO2 network fragment; terminal bonds continue into the solid
. Details.