Density functional theory at the B3LYP/6-311++G(d,p) level is applied to calculate the 29Si NMR chemical shifts of a variety of organosiloxane moieties including monomers or precursors for polymerization and representative segments of organosiloxane polymers or thin films. The calculated shifts of two linear dimethylsiloxane compounds, hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D4), compare well with their known values, having an average error of 3.4 ppm. The same method is applied to structures believed to occur in organosilicate glass thin films deposited using hot-filament chemical vapor deposition (HFCVD) from D3 and D4. The chemical shift at -15 pprn is identified as a cross-linking Si-Si bond between two strained D groups and has not previously been reported. Retention of the strained ringed structure in HFCVD films deposited from D3 is confirmed. The rings are bonded to the matrix through either Si-O or Si-Si bonds, with the latter only becoming prevalent when higher filament temperatures are employed. The strained ring structure is also observed in films deposited from a precursor with a larger unstrained ring structure, D4. These observations suggest that the known gas-phase conversion pathways of D4 to D3 and dimethylsilanone as well as the methyl abstraction reaction from D3 operate, in the HFCVD reaction chemistry.