Exploring the sub-stoichiometric behavior of plutonium mononitride

The intriguing and controversial sub-stoichiometric behavior of plutonium mononitride is investigated here using first-principles calculations combined with special quasirandom structures. It is found that NaCl-type plutonium mononitride is stable for only stoichiometric levels, and the formation enthalpy of plutonium mononitride is in good agreement with others. By comparing with plutonium monocarbide, the main reason for the absence of sub-stoichiometric behavior is the lower N-2p orbital energy, resulting in less hybridization and weaker Pu–N bonds. The weaker Pu–N bonds cannot support the formation of vacancies.