Thermodynamics, structure, and dynamics in room temperature ionic liquids: The case of 1-Butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF 6])

Alessandro Triolo, Andrea Mandanici, Olga Russina, Virginia Rodriguez-Mora, Maria Cutroni, Christopher Hardacre, Mark Nieuwenhuyzen, Hans Jurgen Bleif, Lukas Keller, Miguel Angel Ramos

    Research output: Contribution to journalArticlepeer-review

    Abstract

    A detailed investigation of the phase diagram of 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6]) is presented on the basis of a wide set of experimental data accessing thermodynamic, structural, and dynamical properties of this important room temperature ionic liquid (RTIL). The combination of quasi adiabatic, continuous calorimetry, wide angle neutron and X-ray diffraction, and quasi elastic neutron scattering allows the exploration of many novel features of this material. Thermodynamic and microscopic structural information is derived on both glassy and crystalline states and compared with results that recently appeared in the literature allowing direct information to be obtained on the existence of two crystalline phases that were not previously characterized and confirming the view that RTILs show a substantial degree of order (even in their amorphous states), which resembles the crystalline order. We highlight a strong connection between structure and dynamics, showing the existence of three temperature ranges in the glassy state across which both the spatial correlation and the dynamics change. The complex crystalline polymorphism in [bmim][PF6] also is investigated; we compare our findings with the corresponding findings for similar RTILs. These results provide a strong experimental basis for the exploration of the features of the phase diagram of RTILs and for the further study of longer alkyl chain salts.

    Original languageEnglish
    Pages (from-to)21357-21364
    Number of pages8
    JournalThe Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
    Volume110
    Issue number42
    DOIs
    Publication statusPublished - 26 Oct 2006

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