Predictions of thorium super nitrides and superconductivity under pressure: Ab initio calculations

Abstract

Thorium nitrides have been the topic of intense studies due to their prospective applications as advanced nuclear fuels. The phase diagram of the Th–N scheme, however, continues unknown at low temperatures and extremely high pressures. In this article, we examine the Th–N system's phase diagram up to 300 GPa from the first-principle approach using universal structure predictor: evolutionary Xtallography (USPEX) method. Apart from the experimentally observed phase (ThN, Th2N3, and Th3N4), there are several unique chemical stoichiometries, i.e., ThN3, ThN4, ThN6, ThN8, ThN10, and ThN12 are found to have stability fields on the Th–N phase diagram at pressure of 3.0, 32, 100, 42, 28, and 236 GPa along with previously predicted composition ThN2 at 3.5 GPa. The structural stability of the predicted compositions is further assessed by evaluating the elastic and dynamic stability. Out of all above mentioned compositions, ThN3 is possibly a metastable one at 0 GPa. Electronic structure calculations predict that all newly discovered compositions are metallic except ThN10, which is semi-metallic at high pressures. Further, we predict that ThN4 and ThN6 have high electron–phonon coupling constant of 1.874 and 0.894 with Tc around 21.22 and 25.02 K, respectively, at 100 GPa.