Terahertz spectral change associated with glass transition of poly-ε-caprolactone

We measured absorption spectra of unidirectionally stretched poly-ε-caprolactone (PCL) film in a range from 0.3 to 3.6 THz at temperatures from 10 to 300 K. Several absorption peaks were observed, when the electric field of THz waves was set in directions parallel and perpendicular to the stretching direction. The absorption bandwidths became significantly broad at around 200 K and above at least in two specific peaks. This temperature is close to the glass transition temperature of PCL. Further, it is shown by quantum chemical calculations that all the peaks obtained experimentally originate in skeletal vibrations of PCL. Therefore, it has become clear that a specific feature appears in the THz absorption spectrum of PCL associated with its glass transition