In this article, we present the first ab initio calculations on the novel rigid-rod polymer PIPD using density functional techniques. The behaviour of the molecular chain under strain is studied and the chain modulus agrees excellently with experiment. Two crystal structures are considered and hydrogen bonding networks as proposed from X-ray diffraction measurements are demonstrated to exist. Negligible energy differences were found and both structures could exist at room temperature. The electronic structure reveals a π – π interaction like in graphite, resulting in a weak bonding. The interaction due to the hydrogen bonding network is smaller, however: it leads to a significantly larger bonding energy. As the interchain bonding in PIPD is approximately 3 times the bonding without the network, the improvement in the compressive strength of PIPD compared to PBO and PBT can be attributed to the hydrogen bonding network.
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