Thermodynamics, structure, and dynamics in room temperature ionic liquids: the case of 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6]) |
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Authors: | Triolo Alessandro Mandanici Andrea Russina Olga Rodriguez-Mora Virginia Cutroni Maria Hardacre Christopher Nieuwenhuyzen Mark Bleif Hans-Jurgen Keller Lukas Ramos Miguel Angel |
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Institution: | Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, via La Farina 237, 98123 Messina, Italy. triolo@me.cnr.it |
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Abstract: | A detailed investigation of the phase diagram of 1-butyl-3-methyl imidazolium hexafluorophosphate (bmim]PF(6)]) 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]PF(6)] 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. |
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