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Conformational analysis of poly(butylene terephthalate) (PBT) has been carried out by the refined rotational isomeric state scheme combined with ab initio molecular orbital (MO) calculations and NMR experiments on its model compound, tetramethylene glycol dibenzoate (TetMGDB). Two conformers of TetMGDB, showing intramolecular phenyl–phenyl close contacts, yielded so small free energies at the MP2...