title: A Rayleighian approach for modeling kinetics of ionic transport in polymeric media.
abstract: We report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes from the broadband dielectric spectroscopy measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self-diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreement between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Rajeev
authors.identifier: 0000000194943488
authors.initials: R
authors.lastname: Kumar
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Jyoti P
authors.initials: JP
authors.lastname: Mahalik
authors.affiliation: Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Vera
authors.initials: V
authors.lastname: Bocharova
authors.affiliation: Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: Eric W
authors.initials: EW
authors.lastname: Stacy
authors.affiliation: Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: Catalin
authors.initials: C
authors.lastname: Gainaru
authors.affiliation: Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Tomonori
authors.initials: T
authors.lastname: Saito
authors.affiliation: Department of Physics & Astronomy, Hunter College of the City University of New York, New York, New York 10065, USA.
authors.forename: Mallory P
authors.identifier: 0000000197350741
authors.initials: MP
authors.lastname: Gobet
authors.affiliation: Department of Physics & Astronomy, Hunter College of the City University of New York, New York, New York 10065, USA.
authors.forename: Steve
authors.initials: S
authors.lastname: Greenbaum
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Bobby G
authors.initials: BG
authors.lastname: Sumpter
authors.affiliation: Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: Alexei P
authors.initials: AP
authors.lastname: Sokolov