Intermolecular halogen bonding in complexes of phosphine and dihalogens has been theoretically investigated using explicitly correlated coupled cluster methods and symmetry-adapted perturbation theory. The complexes H3P center dot center dot center dot ClF, H3P center dot center dot center dot BrF, and H3P center dot center dot center dot IF are demonstrated to possess unusually strong interactions that are accompanied by an increase in the induction component of the interaction energy and significant elongation of the X-Y halogen distance on complex formation. The combination of these factors is indicative of Mulliken inner complexes, and criteria for identifying this classification are further developed. The importance of choosing an electronic structure method that describes both dispersion and longer range interactions is demonstrated, along with the need to account for the change in geometry on complexation formation via relaxation energy and overall stabilization energies.