High-resolution FTIR study of the para-terphenyl phase transition at high pressure

High-resolution infrared (IR) spectroscopy has been used to investigate the pressure-induced (0–11 kbar) polymorphic phase transition of crystalline para-terphenyl at low temperature (25 K). A number of doublet bands observed in low-pressure triclinic p-terphenyl were observed to coalesce in the high-pressure monoclinic phase. The coalescing of doublet bands was attributed to changes in factor group (Davydov) splittings associated with the transition from a low-pressure triclinic phase to a high-pressure monoclinic phase. The bands that ‘disappear’ also do not correlate with frequency changes associated with changes in molecular symmetry. Molecular dynamics (MD) simulations at low temperature (20 K) yield a non-planar average molecular structure for the high-pressure monoclinic phase, in contrast to the high-temperature monoclinic phase. The MD simulations also reveal a broadening of the distribution of ring torsion angles near the triclinic–monoclinic phase transition pressure.