Similarly, the Mn 0 Ni defect site corresponds to Mn 2+ (d 5 ) high-spin of -4.5 µ B . The sign change in the magnetisation reflects a spin flip relative to Mn in the bulk and this is related to the complex orbital interactions exchanging the spin information. suggested the spin on Mn 3+ and Mn 2+ should be parallel to that of Ni 2+ due to the oxygen-mediated super-exchange interaction. This coincides with the spin-flip phenomena shown in Table . However, a spin flip is not observed on all defects and there is no clear trend whether a certain spin orientation is preferred. Magnetic interactions are influenced by the point defects and each defect has a complex potential energy surface, meaning that different defect structures and magnetic states may be found, depending on the initial structures, their magnetisation values and the choice of electronic minimisation algorithm. In each case, different degrees of structural perturbation (rattling) and magnetisation initialisations were tested, to aid the location of the true ground state defect. One spin flip usually gives less than 0.1 eV difference in energy. However, multiple spin flips can lead to a large energy change (e.g. ∼1 eV) and give erroneous results. All calculations have been checked and rerun to ensure there are no multiple spin flips on the TM cations.