We investigate the effect of densification on intramolecular and intermolecular chain packing and structural relaxation of four saturated hydrocarbon polymers: poly(ethylene propylene) (PEP), poly(ethylene butene), atactic polypropylene, and head-to-head polypropylene. Within this series, the local chain architecture, specifically the frequency and size of pendant groups, varies. Density changes of rho(0)+/-5%, where rho(0) is the ambient density, are considered at a temperature of 400 K, which is well above the glass transition temperatures of all four polymers. Intramolecular chain packing remains nearly unchanged over this density range, and intermolecular packing shows a tendency towards closer and more efficient packing at higher densities. The effect of density on dynamics depends on the spatial scale considered. Self-intermediate scattering functions, as measured in incoherent quasielastic neutron scattering experiments, are calculated for spatial scales between 2.5 and 20 Angstrom. At length scales less than the closest intermolecular spacing, densification has little effect on mobility. The largest effects are observed in the vicinity of the nearest chain spacing distance, where mobility is decreased and dynamic heterogeneity, as evidenced by the stretching parameter in stretched exponential fits, is increased with densification. At length scales approaching R-g, both effects level off and are slightly less than at spatial scales of interchain packing. The most flexible of the four materials, PEP, is least affected by density changes. (C) 2003 American Institute of Physics.