The radiative decay and radiative charge transfer cross sections for H+ +Rb(5s) collisions are calculated by using the optical potential approach, the semiclassical and the fully quantum-mechanical methods, respectively, for the energy range 10−6−10eV. The radiative association cross sections are obtained by the cross section differences between the radiative decay and radiative charge transfer processes. The relevant molecular data are calculated from the multi-reference single- and double-excitation configuration interaction approach. The emission spectra at resonant and non-resonant energies are analyzed, then the isolated sharp and broad resonances can be identified by their rotational and vibration quantum numbers.