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1.
J Chem Phys ; 148(19): 193815, 2018 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-30307249

RESUMO

Mesoscopic aggregation in aprotic ionic liquids due to the microphase separation of polar and non-polar components is expected to correlate strongly with the physicochemical properties of ionic liquids and therefore their potential applications. The most commonly cited experimental evidence of such aggregation is the observation of a low-q pre-peak in the x-ray and neutron scattering profiles, attributed to the polarity alternation of polar and apolar phases. In this work, a homologous series of phosphonium ionic liquids with the bis(trifluoromethylsulfonyl)imide anion and systematically varying alkyl chain lengths on the phosphonium cation are investigated by small and wide-angle x-ray scattering, dynamic-mechanical spectroscopy, and broadband dielectric spectroscopy. A comparison of the real space correlation distance corresponding to the pre-peak and the presence or absence of the slow sub-α dielectric relaxation previously associated with the motion of mesoscale aggregates reveals a disruption of mesoscale aggregates with increasing symmetry of the quaternary phosphonium cation. These findings contribute to the broader understanding of the interplay of molecular structures, mesoscale aggregation, and physicochemical properties in aprotic ionic liquids.

2.
Soft Matter ; 10(20): 3536-40, 2014 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-24718358

RESUMO

Charge transport and structural dynamics in low molecular weight and polymerized 1-vinyl-3-pentylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids (ILs) are investigated by a combination of broadband dielectric spectroscopy, dynamic mechanical spectroscopy and differential scanning calorimetry. While the dc conductivity and fluidity exhibit practically identical temperature dependence for the non-polymerized IL, a significant decoupling of ionic conduction from structural dynamics is observed for the polymerized IL. In addition, the dc conductivity of the polymerized IL exceeds that of its molecular counterpart by four orders of magnitude at their respective calorimetric glass transition temperatures. This is attributed to the unusually high mobility of the anions especially at lower temperatures when the structural dynamics is significantly slowed down. A simple physical explanation of the possible origin of the remarkable decoupling of ionic conductivity from structural dynamics is proposed.


Assuntos
Imidazóis/química , Líquidos Iônicos/química , Polivinil/química , Espectroscopia Dielétrica , Íons/química , Transição de Fase , Polimerização , Temperatura
3.
Phys Chem Chem Phys ; 15(23): 9300-7, 2013 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-23660993

RESUMO

Broadband dielectric spectroscopy along with a high pressure technique and quantum-mechanical calculations are employed to study in detail the behavior and to reveal the origin of the excess wing (EW) in neat N,N-diethyl-3-methylbenzamide (DEET). Our analysis of dielectric spectra again corroborates the idea that the EW is a hidden ß-relaxation peak. Moreover, we found that the position frequency of the ß peak corresponds to the position of the primitive relaxation of the Coupling Model. We also studied the possible intramolecular rotations in DEET by means of DFT calculation. On that basis we were able to describe the EW as the JG ß-relaxation and find the possible origin of the γ-relaxation visible in DEET dielectric spectra at very low temperatures.

4.
J Phys Chem B ; 114(1): 382-6, 2010 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-19874028

RESUMO

Charge transport and dipolar relaxations in a series of imidazolium-based ionic liquids are studied by means of broadband dielectric spectroscopy. Despite the shift of more than 5 decades in the dielectric spectra upon systematic variation of the anion, scaling with respect to the dc conductivities and the characteristic rates yields a collapsing plot. The dielectric spectra are described at higher frequencies in terms of dipolar relaxations whereas hopping conduction in a random spatially varying energy landscape is quantitatively shown to dominate the spectra at lower frequencies. The beta-relaxations observed for both the precursor and the ionic liquids are assigned to librational motion of the imidazolium ring. The corresponding dielectric strength exhibits a strong dependence on the anion.

5.
Phys Chem Chem Phys ; 11(6): 913-6, 2009 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-19177207

RESUMO

Charge transport and glassy dynamics of a variety of glass-forming ionic liquids (ILs) are investigated in a wide frequency and temperature range by means of broadband dielectric spectroscopy, differential scanning calorimetry and rheology. While the absolute values of dc conductivity and viscosity vary over more than 11 decades with temperature and upon systematic structural variation of the ILs, quantitative agreement is found between the characteristic frequency of charge transport and the structural alpha-relaxation. This is traced back to dynamic glass transition assisted hopping as the underlying mechanism of charge transport.

6.
J Chem Phys ; 129(23): 234511, 2008 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-19102542

RESUMO

Broadband dielectric spectroscopy, differential scanning calorimetry, rheology, and pulsed field gradient-nuclear magnetic resonance (PFG NMR) are combined to study glassy dynamics and charge transport in a homologous series of imidazole-based liquids with systematic variation of the alkyl chain length. The dielectric spectra are interpreted in terms of dipolar relaxation and a conductivity contribution. By applying the Einstein, Einstein-Smoluchowski, and Stokes-Einstein relations, translational diffusion coefficients--in quantitative agreement with PFG NMR measurements--are obtained. With increasing alkyl chain length, it is observed that the viscosity increases, whereas the structural alpha-relaxation rate decreases, in accordance with Maxwell's relation. Between the rate omega(e) of electrical relaxation and the rate omega(alpha) of the structural alpha-relaxation, scaling is observed over more than six decades with a decoupling index of about 2.

7.
Phys Rev E Stat Nonlin Soft Matter Phys ; 77(5 Pt 1): 051202, 2008 May.
Artigo em Inglês | MEDLINE | ID: mdl-18643055

RESUMO

The mechanism of charge transport in the imidazolium-based ionic liquid 1,3-dimethylimidazolium dimethylphosphate is analyzed by combining broadband dielectric spectroscopy (BDS) and pulsed field gradient nuclear magnetic resonance (PFG NMR). The dielectric spectra are dominated-on the low-frequency side-by electrode polarization effects while, for higher frequencies, charge transport in a disordered matrix is the underlying physical mechanism. Using the Einstein and Einstein-Smoluchowski equations enables one to determine-in excellent agreement with direct measurements by PFG NMR-the diffusion coefficient of the charge carriers. By that, it becomes possible to extract from the dielectric spectra separately the number density and the mobilities of the charge carriers and the type of their thermal activation. It is shown that the observed Vogel-Fulcher-Tammann (VFT) dependence of the dc conductivity can be traced back to a similar temperature dependence of the mobility while for the number density an Arrhenius-type thermal activation is found. Extrapolating the latter to room temperature indicates that nearly all charge carriers are participating in the conduction process.

8.
J Chem Phys ; 128(21): 214509, 2008 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-18537435

RESUMO

Broadband dielectric and terahertz spectroscopy (10(-2)-10(+12) Hz) are combined with pulsed field gradient nuclear magnetic resonance (PFG-NMR) to explore charge transport and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. The dielectric spectra are interpreted as superposition of high-frequency relaxation processes associated with dipolar librations and a conductivity contribution. The latter originates from hopping of charge carriers on a random spatially varying potential landscape and quantitatively fits the observed frequency and temperature dependence of the spectra. A further analysis delivers the hopping rate and enables one to deduce--using the Einstein-Smoluchowski equation--the translational diffusion coefficient of the charge carriers in quantitative agreement with PFG-NMR measurements. By that, the mobility is determined and separated from the charge carrier density; for the former, a Vogel-Fulcher-Tammann and for the latter, an Arrhenius temperature dependence is obtained. There is no indication of a mode arising from the reorientation of stable ion pairs.

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