Broadand Dielectric Spectroscopy.PPT

The linear interaction of electromagnetic fields with matter is described by one of Maxwell‘s equations The linear interaction of electromagnetic fields with matter is described by Maxwell‘s equations Dielectric spectra of MMIM Me2PO4 ionic liquid Basic relations between rotational and translational diffusion Predictions to be checked experimentally: Random Barrier Model (Jeppe Dyre et al.) Hopping conduction in a spatially randomly varying energy landscape Analytic solution obtained within Continuous-Time-Random Walk (CTRW) approximation The largest energy barrier determines Dc conduction The complex conductivity is described by: Scaling of invers viscosity 1/? and conductivity s0 with temperature Correlation between translational and rotational diffusion Prediction checked experimentally: Comparison with Pulsed-Field-Gradient NMR and deter-mination of diffusion coefficients from dielectric spectra Predictions checked experimentally: Random Barrier Model (RBM) used to fit the conductivity spectra of ionic liquid (MMIM Me2PO4) The RBM fits quantitatively the data; The invers viscosity 1/? has an identical temperature dependence as s0 and scales with Tg. Correlation between translational and rotational diffusion Stokes-Einstein, Einstein-Smoluchowski and Maxwell relations: Typically: G? ? 0.1 GPa; ? ? .2 nm; as ? .1 nm; J. R. Sangoro et al.(2009) Phys. Chem. Chem. Phys. Stokes-Einstein, Einstein-Smoluchowski and Maxwell relations: Typically: G? ? 0.1 GPa; ? ? .2 nm; as ? .1 nm; J. R. Sangoro et al.Phys. Chem. Chem. Phys, DOI: 0.1039/b816106b,(2009) . 1.: ?c: characteristic (diffusion) rate ??: structural relaxation rate G?: instantaneous shear modulus (~ 108 Pa for ILs), as : Stokes‘ hydrodynamic radius ~?, k: Boltzmann constant, l: characteristic diffusion length ~ .2 nm wc = P w? 2. Prediction: Pulsed-Field-Gradient NMR Broadband Dielectric Spectroscopy