Pressure effect on vibrational frequency and dephasing of 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids.

Raman spectra in the range of the totally symmetric stretching mode of the PF6 anion, νs(PF6), have been measured for 1-alkyl-3-methylimidazolium ionic liquids [CnC1im][PF6], for n = 4, 6, and 8, as a function of pressure at room temperature. The ionic liquids [C6C1im][PF6] and [C8C1im][PF6] remain in an amorphous phase up to 3.5 GPa, in contrast to [C4C1im][PF6], which crystallizes above ~0.5 GPa. Equations of state based either on a group contribution model or Carnahan-Starling-van der Waals model have been used to estimate the densities of the ionic liquids at high pressures. The shifts of the vibrational frequency of νs(PF6) with density observed in [C6C1im][PF6] and in [C8C1im][PF6] have been calculated by a hard-sphere model of a pseudo-diatomic solute under short-range repulsive interactions with the neighboring particles. The stochastic model of Kubo for vibrational dephasing has been used to obtain the amplitude of vibrational frequency fluctuation, <Δω(2)>, and the relaxation time of frequency fluctuation, τc, as a function of density by Raman band shape analysis of the νs(PF6) mode of [C6C1im][PF6] and [C8C1im][PF6].