Proton NMR and deuteron NMR (DMR) have been used to measure hydrogen populations in a series of PECVD a-Si:H,D films. The sharp DMR doublet from Si-D is fitted and subtracted out. The residual spectra then show specific signatures for molecular D-2 and KD. The fitting procedures yield quantitative measures of Si-bonded and molecular species. A particular comparison is made between a pair of films prepared as the powered and unpowered electrodes in the same plasma deposition. Both silicon-bonded and molecular populations are significantly different in the two films and correlate with photoresponse products eta mu r and with IR as well as other materials characterizations.