On the importance of low-frequency modes in predicting pressure-induced phase transitions.

The occurrence of ultra-low frequency oscillation mode as observed by means of periodic DFT calculations at Γ point in a molecular crystal at ambient conditions can be a valuable predictor of imminent pressure-induced phase transition. We illustrate it with a series of polymorphs of diacetyl-pyrenes, for two of which such soft-modes indicated the trajectory of pressure-induced structural reorganization at ≈0.8 GPa. Notably, susceptibility to pressure-induced phase transformations could not be predicted based on material's thermodynamic characteristics, and there were no unequivocal clues in their crystal packing.