[en] In order to reduce the power load onto the target plates detached divertor conditions are often preferred. These are characterized by volume recombination, i.e. three-body and radiative recombination. Due to low T_e (few eV) hydrogen molecules can penetrate into the plasma and may play a role in divertor dynamics. In particular, it was suggested, that molecules may assist the volume recombination process. The role of molecules in the divertor is examined here by a combination of experimental results with plasma edge simulations (B2-EIRENE) and a collisional-radiative model for hydrogen molecules. Spectroscopic diagnostics of the Fulcher transition carried out at the divertor of ASDEX Upgrade yield estimates of molecular hydrogen fluxes and the vibrational population in the ground state in detached and attached hydrogen plasmas. Good agreement with B2-EIRENE is achieved only if vibrational levels are treated as distinct (metastable) particles in the model and if the collisional-radiative model is applied to the electronically excited levels. On this basis the contribution of molecules to plasma recombination was determined to be in the order of a few 10%. The dominant molecular process is the dissociation process via H₂⁺. As a consequence initially detached divertor plasmas can even re-attach if vibrationally resolved molecules are properly included in plasma edge models. A set of B2-EIRENE calculations carried out for ASDEX Upgrade is discussed. In particular the threshold upstream density for detachment was found to be up to a factor 1.5 higher than that originally expected due to these molecular effects. The transferability of the results to deuterium will be discussed