Far Infrared and Raman Spectroscopic Investigations of the Lattice :Modes of Crystalljne Thiophene

Vibrational spectroscopic measurements combined with the lattice statics and lattice mod es calculations have been applied in order to derive the most probable structure of the low temperature (stable) phase V of thiophene (below 112 K). The far infrared spectrum has been recorded from 135 to 30 cm? of this phase of thiophene at 20 K. The low frequency Raman spectrum from 150 to 10 cm" has also been record ed for the phase V at 35 K. From the fact that there is coincidence between lattice mode frequencies observed in the infrared and Raman spectra, one can exclude centrosymmetric space groups. The observations of 20 lattice modes in the Raman spectrum and 14 modes in the FIR spectrum eliminate the possibility of tetragonal symmetry, but the data are consistent with orthorhombic symmetry with the unit cell containing 4 molecules on Cl sites. In spite of the glassy-like transition observed for this phase at 42 K, both spectra bear striking resemblance to the typical low frequency spectra of molecular crystals. Therefore, it is assumed, for the purposes of the static and dynamic studies, that the thiophene in phase V can be considered as an ideally ordered crystal. Calculations of the lattice energy and lattice mode frequencies, based on the atom-atom potential, appear to be most consistent with space group Pca2l (C2v5) which is in agreement with most of the earlier predictions made for the structure of the thiophene phase V. The Raman spectrum of the metastable phase II2 is also given.