A theoretical study on the nature of bonding in several weakly bound radical cation complexes from second and third row hydrides is presented. It is shown that characterization of a two-center three-electron or 2c-3e bond based on its bond distance and binding energy may be misleading in many cases. It is also observed that the ab inito quantum chemical bond order index cannot be taken as a definite signature of a 2c-3e bond. Instead, it is suggested that appropriate localized molecular orbital need be used to test the presence of a 2c-3e bond. Localization of relevant molecular orbital in the 2c-3e bonded systems also suggests that the newly formed bond is of sigma character. Normal-mode analysis is performed to identify the stretching mode in the 2c-3e bonded radical cation complexes. Geometry optimizations are carried out at MP2 and restricted open shell Becke's half-and-half (BHH) nonlocal exchange and Lee-Yang-Parr (LYP) nonlocal correlation functionals (BHHLYP) with 6-31++G(d,p) basis set. Hessian calculations are done at the BHHLYP level. Excited-state calculations are performed following the configuration interaction with single electron excitation (CIS) method, and the lowest optical transition wavelengths (lambda(max)) in the 2c-3e bonded complexes are reported. BHHLYP functionals have been found to describe the 2c-3e bonded systems well within the restricted open shell formalism.