|The molecular geometries and conformational energies of model molecules of poly(vinylidene fluoride) (PVDF) have been determined from high-level quantum chemistry calculations and have been used in parametrization of a six-state rotational isomeric state (RIS) model for PVDF. The model molecules investigated were 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3,5,5,5-octofluoropentane, 2,2,4,4-tetrafluoropentane, and 2,2,4,4,6,6-hexafluoroheptane (HFH). Analysis of the conformations of these molecules revealed split trans minima (t+ = 195°, t- = 165°), as was seen in previous studies of perfluoroalkanes. In contrast, the gauche minima, which split in perfluoroalkanes, did not do so in the PVDF model compounds. The lowest energy conformer of HFH, g+g+g+g+, was found to be at least 0.4 kcal/mol lower in energy per backbone dihedral than any of the conformers of HFH resembling crystalline polymorphs of PVDF, indicating that intermolecular interactions are important in stabilizing conformations of PVDF in the crystalline phases. A six-state RIS model was able to accurately reproduce the conformer energies of the PVDF model compounds. The RIS analysis revealed that, as in n-alkanes and perfluoroalkanes, the trans conformation of the backbone dihedral is intrinsically lower in energy than the gauche conformation in the PVDF model compounds. However, very large unfavorable second-order interactions between fluorine atoms occur in ?CH2? centered t+t+ sequences and, to a lesser extent, t+g+ and t+g- sequences. The quantum chemistry based RIS model yielded a characteristic ratio for PVDF in good agreement with experiment, but with significantly different conformer populations than predicted by earlier RIS models, including a much higher gauche probability. The high gauche probability of 65% for unperturbed PVDF chains (at 463 K), greater than that for poly(ethylene) and much greater than that for poly(tetrafluoroethylene), is a consequence of the unfavorable second-order interactions occurring in ?CH2? centered sequences containing trans conformations.