Restricted active space simulations are shown to accurately reproduce and characterise both O K-edge and U M_4,5-edge spectra of uranyl in excellent agreement with experimental peak positions and are extended to the Np analogue. Analysis of bonding orbital composition in the ground and O K-edge core-excited states demonstrates that metal contribution is underestimated in the latter. In contrast, An M_4/5-edge core-excited states produce bonding orbital compositions significantly more representative of those in the ground state. Quantum Theory of Atoms in Molecules analysis is employed to explain the discrepancy between K- and M-edge data and demonstrates that the location of the core-hole impacts the pattern of electron localisation in core-excited states. An apparent contradiction to this behaviour in neptunyl is rationalised in terms interelectronic repulsion between the unpaired 5f electron and the excited core-electron.