Reactivity of Ru oxides with air radiolysis products investigated by theoretical calculations

•Reactive pathways leading to the formation of volatile ruthenium trioxide and tetroxide substances with air radiolysis products were elucidated.•Relativistic correlated quantum chemical calculations provided the involved kinetic parameters.•Finding results corroborate the experimental observations of ruthenium formation under steam atmosphere containing nitrous and nitrogen oxides. Quantitative predictions of the release of volatile radiocontaminants of ruthenium (Ru) in the environment from either nuclear power plants (NPP) or fuel recycling accidents present significant uncertainties while estimated by severe accidents nuclear analysis codes. Observations of Ru from either experimental or modeling works suggest that the main limitations relate to the poor evaluation of the kinetics of gaseous Ru in the form of RuO3 and RuO4. This work presents relativistic correlated quantum chemical calculations performed to determine the possible reactions pathways leading to the formation of gaseous Ru oxides under NPP severe accident conditions, as a result of reactions of RuO2 gaseous with air radiolysis products, namely nitrous and nitrogen oxides. The geometries of the relevant species were optimized with the TPSSh-5%HF functional of the density, while the total electronic energies were computed at the CCSD(T) level with extrapolations to the complete basis set CBS limit. The reaction pathways were fully characterized by localizing the transition states and all intermediate structures using the internal coordinate reaction algorithm (IRC). The rate constants were determined over the temperature range 250-2500K. It is revealed that the less kinetically limiting pathway to form Ru gaseous fraction is the oxidation of Ru by nitrogen oxide, corroborating experimental observations.