Effects of magnetic excitations and transitions on vacancy formation: Cases of fcc Fe and Ni compared to bcc Fe

Vacancy is one of the most frequent defects in metals. We study the impacts of magnetism on vacancy formation properties in fcc Ni, and in bcc and fcc Fe, via density functional theory (DFT) and effective interaction models combined with Monte Carlo simulations. Overall, the predicted vacancy formation energies and equilibrium vacancy concentrations are in good agreement with experimental data, available only at the high-temperature paramagnetic regime. Effects of magnetic transitions on vacancy formation energies are found to be more important in bcc Fe than in fcc Fe and Ni. The distinct behavior is correlated to the relative roles of longitudinal and transversal spin excitations. At variance with the bcc-Fe case, we note a clear effect of longitudinal spin excitations on the magnetic free energy of vacancy formation in fcc Fe and Ni, leading to its steady variation above the respective magnetic transition temperature. Below the N\'eel point, such effect in fcc Fe is comparable but opposite to the one of the transversal excitations. Regarding fcc Ni, although neglecting the longitudinal spin excitations induces an overestimation of the Curie temperature by 220 K, no additional effect is visible below the Curie point. The distinct effects on the three systems are closely linked to DFT predictions of the dependence of vacancy formation energy on the variation of local magnetic-moment magnitudes and orientations.