Electron induced dissociation of physisorbed H2, HD, and D2 proceeds, as we observe in electron energy-loss measurements of the resulting atomic species, with a high quantum efficiency via the 2Σg+ core excited electron scattering resonances. We find that the predominant decay of the temporary H2- state to the neutral excited 3Σu+ parent state, which is intramolecularly antibonding, provides a sufficiently long-lived channel for dissociation to occur with high probability, even in the proximity of a metal surface.