Thermodynamic and kinetic stabilities of CO2 oligomers

Density-functional and coupled cluster calculations suggest that the stability, against unimolecular dissociation, of the cyclic D-3h trimer of CO2, 1,3,5-trioxetanetrione, is greater than all but one other chemically bound oligomer of CO2. It requires far less energy to produce, on a per CO2 basis, than the low-symmetry cyclic 1,2 dioxetanedione dimer, but its kinetic stability against unimolecular dissociation is much lower. The extreme stability of the dimer, which makes it an excellent intermediate in chemiluminescence, is caused by an extreme range of geometric change to its transition state leading to a trapezoidal potential energy surface. The thermodynamically more stable trimer affords a low pressure pathway from molecular carbon dioxide to the extended covalent structure at high pressure. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4797465]