To characterise and define what can be considered an ion-pair from a theoretical perspective, an exhaustive analysis of the interactions established within the different systems under study has been carried out. First, to investigate the physical origins of the interactions involved, an analysis of localised molecular orbital energy decomposition (LMO-EDA) was performed, which allows the determination of the contribution of the different energy components to the global stability of the systems (Figure ). This approach has been extensively used in the literature to describe non-covalent interactions, such as those reported in the present paper. These contributions will provide insight into the nature and magnitude of interactions within the systems under study. From the analysis of the various contributions to the total energy, it is evident that the electrostatic term corresponding to a quasiclassical Coulombic interaction between monomers constitutes the major component of the overall energy in these systems. This observation further reinforces the fundamental nature of the electrostatic interactions in governing the stability and behaviour of ionic compounds. A similar trend was observed across both types of systems, encompassing both ionic and N(CF 3 ) 4 -X complexes. However, it is noteworthy that the total energy and the electrostatic term associated with the N(CF 3 ) 4 -X systems are approximately half the corresponding values observed for the proper ionic compounds in the ion-pair configuration, emphasising that although both cases involve electrostatic interactions, the latter exhibits remarkably weaker interactions in comparison, being the distances between anion and cation increased accordingly. More importantly, the dispersion term becomes more negative in the case of N(CF 3 ) 4 -X salts, being almost negligible in the case of pure ionic compounds, but the repulsion term is lower since the distance between the anion and the cation increases sensibly.