Density Functional Theory (DFT) is, in principle, a powerful tool in the modeling of high-valence redox reactions in cathode materials and can help to examine the thermodynamics of oxygen dimerisation in the bulk of LiNiO 2 . However, care must be taken to ensure that the starting structures used do not bias the calculations toward local minima which do not adequately describe the stable redox products. Energetic minima for high-valent redox processes in intercalation cathodes are generally found to involve structural transformations . To address these challenges and investigate the possibility of bulk molecular O 2 formation in LiNiO 2 we adopt a model system: fully delithiated R 3m NiO 2 . We then perform a structure search inspired by recent methodological advancements in the search for ground-state point defect structures, employing chemically informed but otherwise stochastic approaches to the generation of trial structures that are then subsequently relaxed using hybrid-DFT .