Atomistic calculations on the high-temperature condis phase of poly(trans-1,4-butadiene) (PTBD)

Abstract

The structure of the low-temperature phase of poly(trans-1,4-butadiene) was calculated by means of semiempirical atomistic potentials. Without using any symmetry assumptions there is good agreement with experimental data. In order to understand the high-temperature phase, packing energy calculations were performed with different chain conformations. There are a great number of possible packing modes. They show an approximately linear relation between defect volume and defect energy. The results of these calculations are taken as a basis for a thermodynamic treatment (cooperative pair theory) of the phase transition. The experimental transition enthalpy can only partially be explained by intermolecular interactions, and the defect energy of the various intramolecular equilibrium conformations is not sufficient to explain the difference. A refined treatment with a simultaneous inter-and intramolecular minimization of the energy reveals that the chains are not in their intramolecular equilibrium state. This results in an additional intramolecular defect energy which seems to lead to an understanding of the experimental transition data.