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The complexity of the phase diagram of a representative room temperature ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF(6)]) is explored by means of Raman spectroscopy at high pressure (up to 1000 MPa) and high temperature (from room temperature to 100 °C) conditions. The first experimental evidence of the existence of a second crystalline phase for this salt at high pressure conditions is provided. By comparing the low frequency vibrational bands for the liquid state and the two observed crystalline phases, we confirm the scenario that considers the crystal polymorphism in this class of materials as a consequence of the rotational isomerism of the butyl chain. Furthermore the pressure dependence of other vibrational bands indicates the existence of a structural rearrangement across p≈ 50 MPa at ambient temperature.

Structural organization and phase behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate: an high pressure Raman spectroscopy study