An nb initio density functional technique (AIMPRO) has been employed to inv
estigate the structure, vibrational properties, and dissociation mechanisms
of CO30, the important radical anion CO3- and the interaction of this spec
ies with the graphite basal plane. The results are discussed in the context
of the radiolytic oxidation of graphite: a process of relevance to the Bri
tish nuclear industry, which relies for the most part on graphite-cored, CO
2-cooled reactors. The radiation field splits coolant molecules and produce
s, amongst other things, a very reactive radical anion CO3-, which has been
suggested as the main agent for the accelerated oxidation of graphite. Thi
s paper shows that CO3- binds strongly to graphite after combining with an
electronic hole and forming a long and strong ionic bond. It still remains
mobile on the basal plane and can diffuse to a graphite edge and oxidize it
.