Steroids generally form protonated adduct ions and metal adducts with sodium and potassium from naturally occurring salts during electrospray ionization. Deliberate cationization is also possible for example with transition metal ions by simply adding an optimized concentration of the transition metal salt to the electrospray solvent. The functional group(s) to which the metal ions get attached to the steroid molecule during the electrospray event is difficult to predict. However, it is important to know the geometry-optimized structures of adducts that are needed to predict drift times in ion mobility spectrometry. In addition, the results could also shed light on what metal ions are best suited for a particular group of molecules.