The enhancement of theH2(&ngr;″)vibrational distribution observed in the medium‐density hydrogen discharge of Eenshuistra and co‐workers is investigated theoretically as a function of different excitation processes. The observed fivefold enhancement of the&ngr;″=5population with increasing discharge current is reproduced in the model. Principal excitations generating this enhancement areH+3surface recombination and fast‐electron excitation. Atom‐surface recombination may be a principal contributor near the&ngr;″=1portion of the spectrum.