The recombination and dissociation of H+2and H+3ions incident upon metal surfaces leads to H, H2(v‘), and H−products rebounding from the surface. A four‐step model for H+2‐ion recombination generates H2(v‘) via resonant electron capture through theb 3&Sgr;+uandX 1&Sgr;+gstates. A molecular trajectory analysis provides final‐state H2(v‘) distributions for incident energies of 1, 4, 10, and 20 eV. The calculated H2@B:H+2yields compare favorably with the observed yields. A similar four‐step model for incident H+3proceeds via resonant capture to form the H3(2p 2E’→2p 2A1) ground state, in turn dissociating into H+H2(v_‘), with the fragment molecule rebounding to give the final H2(v‘) distribution. Comparing the final populationsv‘≥5 for incident H+2or H+3shows that the H+3ion will be more useful than H+2for H−generation via dissociative attachment. Molecular ions incident upon low‐work‐function surfaces generate additional H2(v‘) via resonant electron capture through excited electronic states and provide two additional sources of H−production: Direct H−production by H dissociation products rebounding from the surface and H−production through the formation of H−2in the surface selvage that in turn dissociates into H+H−. The H−2in the selvage is formed by resonant capture to the low‐lying vibrational levels of H2(v‘), and complements dissociative attachment to high‐lying levels in the discharge. The H, H2(v‘), and H−yields are inventoried for H+3incident upon barium surfaces.