Quantum Modelling of Ruthenium Chemistry in the field of Nuclear Power Plant Safety

During a severe accident (SA) occurring to a pressurized water reactor (PWR), fission products (FPs) are released from the nuclear fuel and may reach the nuclear containment building. Among the FPs, ruthenium (Ru) is of particular interest due to its ability to form volatile oxide compounds in highly oxidizing conditions combined with its high radiotoxicity (¹⁰³Ru and ¹⁰⁶Ru isotopes) at middle term after the accident. Uncertainties concerning evaluation releases of Ru are important and some R and D efforts are led to get a better understanding of ruthenium chemistry in such conditions. The thermodynamic database on ruthenium species used to estimate these releases shows some discrepancies for most ruthenium oxides and for other species such as oxyhydroxides, data are scarce and not reliable, calling for quantum chemical calculations. The most suitable approach corresponds to TPSSh-5%HF for geometry optimization, followed by CCSD(T) for the calculation of the total electronic energies. The energetics are combined with statistical physics to obtain the thermochemical properties of ruthenium oxides and ruthenium oxyhydroxide species as the latter may play an important role on the transport of ruthenium in the primary circuit due to high steam content. The revised thermodynamic database is then used to predict which species are most stable in representative severe accident conditions. Next, kinetic calculations are also performed to obtain pathways of formations for ruthenium trioxide and tetraoxide gaseous compounds, which are the most stable Ru volatile species in steam/air atmospheres. (author)