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Journal ArticleDOI

Medium decoupling of dynamics at temperatures ~100 K above glass-transition temperature: a case study with (acetamide + lithium bromide/nitrate) melts.

02 May 2012-Journal of Chemical Physics (American Institute of Physics)-Vol. 136, Iss: 17, pp 174503-174503
TL;DR: Estimated experimental dynamic Stokes shift for coumarin 153 in these mixtures lies in the range, 1000 < Δν(t)/cm(-1) < 1700, and is in semi-quantitative agreement with predictions from the authors' semi-molecular theory.
Abstract: Time-resolved fluorescence Stokes shift and anisotropy measurements using a solvation probe in [0.78CH(3)CONH(2) + 0.22{f LiBr + (1-f) LiNO(3)}] melts reveal a strong decoupling of medium dynamics from viscosity. Interestingly, this decoupling has been found to occur at temperatures ∼50-100 K above the glass transition temperatures of the above melt at various anion concentrations (f(LiBr)). The decoupling is reflected via the following fractional viscosity dependence (η) of the measured average solvation and rotation times ( and , respectively): ∝ (η∕T)(p) (x being solvation or rotation), with p covering the range, 0.20 than for , indicating a sort of translation-rotation decoupling. Multiple probes have been used in steady state fluorescence measurements to explore the extent of static heterogeneity. Estimated experimental dynamic Stokes shift for coumarin 153 in these mixtures lies in the range, 1000 < Δν(t)/cm(-1) < 1700, and is in semi-quantitative agreement with predictions from our semi-molecular theory. The participation of the fluctuating density modes at various length-scales to the observed solvation times has also been investigated.
Citations
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Journal ArticleDOI
TL;DR: A detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in deep eutectic solvents, and highlights recent research efforts to elucidate the next steps needed to develop a fundamental framework needed for a deeper understanding.
Abstract: Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These materials are promising for applications as inexpensive "designer" solvents exhibiting a host of tunable physicochemical properties. A detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding is postulated as the root cause of their melting point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework needed for a deeper understanding of DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies promising research thrusts aligned with the advancement of the field toward predictive models and fundamental understanding of these solvents.

911 citations

Journal ArticleDOI
TL;DR: Representative all-atom molecular dynamics simulations of (CH3CONH2 + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in terms of temporal heterogeneity and amide clustering in these multi-component melts.
Abstract: Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH2 + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH2) considered are acetamide (CH3CONH2), propionamide (CH3CH2CONH2), and butyramide (CH3CH2CH2CONH2); the electrolytes (LiX) are lithium perchlorate (LiClO4), lithium bromide (LiBr), and lithium nitrate (LiNO3). Differential scanning calorimetric measurements reveal glass transition temperatures (Tg) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual Tgs. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH3CONH2 + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in terms of temporal heterogeneity and amide clustering in these multi-component melts.

84 citations

Journal ArticleDOI
TL;DR: Dielectric relaxation measurements in the frequency range 0.2 ≤ ν/GHz ≤ 50 have been carried out for neat molten acetamide and six different (acetamide + electrolyte) deep eutectic solvents for investigating ion effects on DR dynamics in these ionic DESs, revealing pronounced anion and cation effects.
Abstract: Dielectric relaxation (DR) measurements in the frequency range 0.2 ≤ ν/GHz ≤ 50 have been carried out for neat molten acetamide and six different (acetamide + electrolyte) deep eutectic solvents (DESs) for investigating ion effects on DR dynamics in these ionic DESs. Electrolytes used are lithium salts of bromide (LiBr), nitrate (LiNO3), and perchlorate (LiClO4); sodium salts of perchlorate (NaClO4) and thiocyante (NaSCN); and potassium thiocyanate (KSCN). With these electrolytes acetamide forms DESs approximately at an 80:20 mol ratio. Simultaneous fits to the measured permittivity (e′) and loss (e″) spectra of these DESs at ∼293 K require a sum of four Debye (4-D) processes with relaxation times spread over picosecond to nanosecond regime. In contrast, DR spectra for neat molten acetamide (∼354 K) depict 2-D relaxation with time constants ∼50 ps and ∼5 ps. For both the neat and ionic systems, the undetected dispersion, e∞ – n(D)2, remains to be ∼3–4. Upon comparison, measured DR dynamics reveal pronounced anion and cation effects. Estimated static dielectric constants (e0) from fits for these DESs cover the range 12 < e0 < 30 and are remarkably lower than that (e0 ∼ 64) measured for molten acetamide at ∼354 K. Hydrodynamic effective rotation volumes (Veff) estimated from the slowest DR relaxation time constants vary with ion identity and are much smaller than the molecular volume of acetamide. This decrease of e0 and Veff is attributed respectively to the pinning of acetamide molecules by ions and orientation jumps and undetected portion to the limited frequency coverage employed in these measurements

73 citations

Journal ArticleDOI
TL;DR: This paper summarizes the dielectric results of various PILs reflecting recent advances in this field and concludes that protic ionic liquids are viable candidates for fuel cells.
Abstract: Protic ionic liquids (PILs) are key materials for a wide range of emerging technologies. In particular, these systems have long been envisioned as promising candidates for fuel cells. Therefore, in recent years special attention has been devoted to thorough studies of these compounds. Amongst others, dielectric properties of PILs at ambient and elevated pressure have become the subject of intense research. The reason for this lies in the role of broadband dielectric spectroscopy in recognizing the conductivity mechanism in protic ionic systems. In this paper, we summarize the dielectric results of various PILs reflecting recent advances in this field.

73 citations


Additional excerpts

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Journal ArticleDOI
TL;DR: Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents made of acetamide and urea have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutsenic solvent systems.
Abstract: Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH3CONH2) and urea (NH2CONH2) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH3CONH2 + (1 − f)NH2CONH2] have been studied in a temperature range of 328-353 K which is ∼120-145 K above the measured glass transition temperatures (∼207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probe solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (∼70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α2) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.

72 citations

References
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Journal ArticleDOI
TL;DR: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations as mentioned in this paper.
Abstract: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations. Revisions are based on new structural data, empirical bond strength-bond length relationships, and plots of (1) radii vs volume, (2) radii vs coordination number, and (3) radii vs oxidation state. Factors which affect radii additivity are polyhedral distortion, partial occupancy of cation sites, covalence, and metallic character. Mean Nb5+-O and Mo6+-O octahedral distances are linearly dependent on distortion. A decrease in cation occupancy increases mean Li+-O, Na+-O, and Ag+-O distances in a predictable manner. Covalence strongly shortens Fe2+-X, Co2+-X, Ni2+-X, Mn2+-X, Cu+-X, Ag+-X, and M-H- bonds as the electronegativity of X or M decreases. Smaller effects are seen for Zn2+-X, Cd2+-X, In2+-X, pb2+-X, and TI+-X. Bonds with delocalized electrons and therefore metallic character, e.g. Sm-S, V-S, and Re-O, are significantly shorter than similar bonds with localized electrons.

51,997 citations

Journal ArticleDOI
TL;DR: In this paper, the locus of the dielectric constant in the complex plane was defined to be a circular arc with end points on the axis of reals and center below this axis.
Abstract: The dispersion and absorption of a considerable number of liquid and dielectrics are represented by the empirical formula e*−e∞=(e0−e∞)/[1+(iωτ0)1−α]. In this equation, e* is the complex dielectric constant, e0 and e∞ are the ``static'' and ``infinite frequency'' dielectric constants, ω=2π times the frequency, and τ0 is a generalized relaxation time. The parameter α can assume values between 0 and 1, the former value giving the result of Debye for polar dielectrics. The expression (1) requires that the locus of the dielectric constant in the complex plane be a circular arc with end points on the axis of reals and center below this axis.If a distribution of relaxation times is assumed to account for Eq. (1), it is possible to calculate the necessary distribution function by the method of Fuoss and Kirkwood. It is, however, difficult to understand the physical significance of this formal result.If a dielectric satisfying Eq. (1) is represented by a three‐element electrical circuit, the mechanism responsible...

8,409 citations

Journal ArticleDOI
TL;DR: Fractional kinetic equations of the diffusion, diffusion-advection, and Fokker-Planck type are presented as a useful approach for the description of transport dynamics in complex systems which are governed by anomalous diffusion and non-exponential relaxation patterns.

7,412 citations

Journal ArticleDOI
Gordon S. Fulcher1
TL;DR: In this article, the authors compared the results given by English with those of Washburn, Shelton and Libman, indicating a discrepancy in the absolute values of log10 viscosity amounting to 0.6.
Abstract: Viscosity of Simple Soda-Silicate Glasses, 500° to 1400°C Comparison of the results given by English with those of Washburn, Shelton and Libman, indicates a discrepancy in the absolute values of log10 viscosity amounting to 0.6, those of Washburn et al., being relatively too high. If correction for this is made, the isothermal curves of log10 viscosity as a function of soda content are smooth up to 50% Na2O, showing no inflection. The observations as a function of temperature T are all represented within accidental error by an equation of the type log10η=−A+B× 103/ (T−T0) where all three constants vary regularly with the composition. Change of Viscosity of Glass (6SiO2, 2Na2O) due to Molecular Substitution of CaO, MgO and Al2O3 for Na2O The effect is clearly brought out by plotting (from the results of English) the change of log10n due to the substitution as a function of temperature. The curves each show a sharp bend at a temperature between 840° and 1050°C, which is designated the aggregation temperature Ta. If we divide these curves by the corresponding percentage substituted, we get curves for each oxide which are straight and parallel below the aggregation temperatures, the slopes (increase of change of log10n per 100°C) being −0.056 (CaO), −0.055 (MgO), −0.018 (Al2O3) per per cent oxide substituted. For substitution of 1/2 molecule the slopes are −0.325 (CaO), −0.23 (MgO) and −0.18 (Al2O3) per 100°. At the aggregation temperature the change of log10n per per cent is a minimum, 0.03 to 0.06 for CaO, 0.12 for MgO, 0.07 for Al2O3. Evidence of Aggregation in Glasses, from Viscosity Measurements . The sharp bends in the plots of change of log10n due to substitution of an oxide for Na2O, suggest the beginning of molecular aggregation at these temperatures. These aggregation temperatures are close to the devitrification temperatures, but the effect on the viscosity curves cannot be due to actual devitrification since it does not change with time. Taking the aggregation temperatures as equal to devitrification temperatures, additional isotherms are roughly sketched into the equilibrium triangle of the system Na2O─CaO─SiO2. Change of Viscosity of Glass (4SiO2, 2Na2O) due to Substitution of B2O3 for SiO2 The change of log10n (from the results of English) is plotted as a function of temperature, and also the change of log10n per per cent B2O3. The curves are more complex than for the substitution for Na2O.

3,596 citations