Molecular symmetry change of perfluoro-n-alkanes in 'Phase I' monitored by infrared spectroscopy

Phase diagram of polytetrafluoroethylene (PTFE) comprises four regions. Phases II and IV are characterized by twisted perfluoroalkyl (R_f) chains having different twisting rate of 13/6 and 15/7, respectively, while Phase III is characterized by a planer trans-zigzag molecular skeleton like a normal alkyl chain. These are confirmed by X-ray and electron diffraction and have already been established. Unlike these, Phase I is left an unresolved matter. This phase is complicated indeed and is not symbolized by a single molecular structure. At an ambient pressure, Phase I is the temperature region above 30 ºC (303 K), and the helical molecular structure is supposed to be gradually untwisted with an elevating temperature. This untwisting image is roughly suggested by the diffraction, neutron scattering, and thermal expansion techniques, but the conventional approaches have all experimental limitations because the untwisting accompanies disorder (or defect) in the twist along the chain. To explore the transition between two different helical structures of the R_f chain having disordered structures, vibrational spectroscopic techniques are expected to be an alternative approach. For infrared spectroscopy, for example, the twisting rate of the molecule is simply recognized as a degree of molecular symmetry. Here, we show that the band progression peaks of the CF₂ symmetric stretching vibration mode are quite sensitive and useful for pursuing the molecular symmetry change in Phase I for both peak intensity and position using perfluoro-n-alkanes having different chain length covering both even and odd number of the CF₂ groups.