First-Principles Calculation of Phonon and Schottky Heat Capacities of Plutonium Dioxide

Plutonium dioxide (PuO2) is a key ingredient of mixed oxide (MOX) and advanced nuclear fuels. Its thermophysical data is crucial in understanding the high-temperature behaviors of nuclear fuels. In particular, the high-temperature heat capacity is of great importance for their safety and performance analyses. Here, we evaluate the main contributions to the heat capacity of PuO2 from 0 to 1400 K through suitable first-principles calculations. Consequently, we successfully obtain a temperature dependence in good agreement with experimental measurements. This success mainly results from accurate calculations of the Schottky heat capacity caused by the excited levels of f-electrons of Pu. Our calculations resolve the mystery of why previous works failed to reproduce the measurement data. This study extends the possibility of performing simulation-based nuclear-fuel research instead of difficult measurements.