Dielectric Properties Of Solvent Research Articles

A screening of results on the decay length in concentrated electrolytes.

Screening of electrostatic interactions in room-temperature ionic liquids and concentrated electrolytes has recently attracted much attention as surface force balance experiments have suggested the emergence of unanticipated anomalously large screening lengths at high ion concentrations. Termed underscreening, this effect was ascribed to the bulk properties of concentrated ionic systems. However, underscreening under experimentally relevant conditions is not predicted by classical theories and challenges our understanding of electrostatic correlations. Despite the enormous effort in performing large-scale simulations and new theoretical investigations, the origin of the anomalously long-range screening length remains elusive. This contribution briefly summarises the experimental, analytical and simulation results on ionic screening and the scaling behaviour of screening lengths. We then present an atomistic simulation approach that accounts for the solvent and ion exchange with a reservoir. We find that classical density functional theory (DFT) for concentrated electrolytes under confinement reproduces ion adsorption at charged interfaces surprisingly well. With DFT, we study confined electrolytes using implicit and explicit solvent models and the dependence on the solvent's dielectric properties. Our results demonstrate how the absence vs. presence of solvent particles and their discrete nature affect the short and long-range screening in concentrated ionic systems.

Quantum optimal control theory for solvated systems.

In this work, we generalize the quantum optimal control theory (QOCT) of molecules subject to ultrashort laser pulses to the case of solvated systems, explicitly including the solvent dielectric properties in the system's quantum Hamiltonian. A reliable description of the solvent polarization is accounted for within the polarizable continuum model (PCM). The electron dynamics for the molecules in solution is coupled with the dynamics of the surrounding polarizable environment, which affects the features of the optimized laser pulse. To illustrate such effects, numerical applications of the developed method to the study of optimal population of selected excited states of two molecular solvated systems are presented and discussed.

Microfluidic biochemical sensor based on circular SIW‐DMS approach for dielectric characterization application

This work proposes an advancement of microwave planar resonator sensor with high sensitivity for microfluidic dielectric characterization. The physical design was employed based on circular substrate integrated waveguide (CSIW) with an integration of defected microstrip structure (DMS). This approach can be applied to accelerate the dielectric detection, structure miniaturization and material differentiation. The presented sensor operates based on variations in the dielectric properties of solvents in the vicinity of a planar open-ended microstrip resonator device. Further analysis in volume and concentration were performed to validate the reliability of the sensor. Validation and functionality of the sensor were investigated by experimental and results comparison. A mathematical model was developed to determine the dielectric constant and the loss tangent of the microfluidic samples. The average error detection has a lower percentage value of 0.11% by comparison to the commercial and ideal dielectric properties of the aqueous samples. The maximum relative error detection, ±0.37% implied better accuracy compared to the existing resonator sensors with more than 400 of the Q-factor. The proposed CSIW-DMS sensor was found to give higher accuracy and detection response; besides easier to fabricate, and compatible for integration with other electronic components in an RF sensor for variety of applications.

Thermodynamic Properties of Aqueous Species Calculated Using the HKF Model: How Do Different Thermodynamic and Electrostatic Models for Solvent Water Affect Calculated Aqueous Properties?

Thermodynamic properties of aqueous species are essential for modeling of fluid-rock interaction processes. The Helgeson-Kirkham-Flowers (HKF) model is widely used for calculating standard state thermodynamic properties of ions and complexes over a wide range of temperatures and pressures. To do this, the HKF model requires thermodynamic and electrostatic models of water solvent. In this study, we investigate and quantify the impact of choosing different models for calculating water solvent volumetric and dielectric properties, on the properties of aqueous species calculated using the HKF model. We identify temperature and pressure conditions at which the choice of different models can have a considerable effect on the properties of aqueous species and on fluid mineral equilibrium calculations. The investigated temperature and pressure intervals are 25–1000°C and 1–5 kbar, representative of upper to middle crustal levels, and of interest for modeling ore-forming processes. The thermodynamic and electrostatic models for water solvent considered are: Haar, Gallagher and Kell (1984), Wagner and Pruß (2002), and Zhang and Duan (2005), to calculate water volumetric properties, and Johnson and Norton (1991), Fernandez and others (1997), and Sverjensky and others (2014), to calculate water dielectric properties. We observe only small discrepancies in the calculated standard partial molal properties of aqueous species resulting from using different water thermodynamic models. However, large differences in the properties of charged species can be observed at higher temperatures (above 500°C) as a result of using different electrostatic models. Depending on the aqueous speciation and the reactions that control the chemical composition, the observed differences can vary. The discrepancy between various electrostatic models is attributed to the scarcity of experimental data at high temperatures. These discrepancies restrict the reliability of the geochemical modeling of hydrothermal and ore formation processes, and the retrieval of thermodynamic parameters from experimental data at elevated temperatures and pressures.

Vapor sensing performances of PVDF nanocomposites containing titanium dioxide nanotubes decorated multi-walled carbon nanotubes

Inorganic nanocarbon hybrid materials are good alternatives for superior electrochemical performance and specific capacitance to their traditional counterparts. Nanocarbons act as a good template for the growth of metal nanoparticles on it and their hybrid combinations enhance the charge transport and rate capability of electrochemical materials without sacrificing the specific capacity. In this study, titanium dioxide nanotubes (TNT) are synthesized hydrothermally in the presence of multi-walled carbon nanotubes (MWCNT) where the latter acts as base template material for the metal oxide nanotube growth. The MWCNT–TNT hybrid material possesses very high dielectric strength and this is used to enhance the dielectric property of the polymer polyvinyledene fluoride (PVDF). Solution mixing was used to prepare the PVDF/MWCNT–TNT nanocomposites by varying the filler concentrations from 0.5 to 2.5 wt%. Excellent vapor sensing was noticed for the PVDF nanocomposites with different rate of response towards commonly used laboratory solvents. The composites and the fillers were characterized for its morphology and structural properties using scanning and transmission electron microscopy, X-ray diffraction studies and infrared spectroscopy. Vapor sensing was measured as relative resistance variations against the solvent vapors, and the dielectric properties of the composites were measured at room temperature during the frequency 102–107 Hz. Experimental results revealed the influence of filler synergy on the properties of PVDF and the enhancement in the solvent vapor detectability and dielectric properties reflects the ability of these composite films in flexible vapor sensors and in energy storage.

How good is the generalized Langevin equation to describe the dynamics of photo-induced electron transfer in fluid solution?

The dynamics of unimolecular photo-triggered reactions can be strongly affected by the surrounding medium for which a large number of theoretical descriptions have been used in the past. An accurate description of these reactions requires knowing the potential energy surface and the friction felt by the reactants. Most of these theories start from the Langevin equation to derive the dynamics, but there are few examples comparing it with experiments. Here we explore the applicability of a Generalized Langevin Equation (GLE) with an arbitrary potential and a non-Markovian friction. To this end, we have performed broadband fluorescence measurements with sub-picosecond time resolution of a covalently linked organic electron donor-acceptor system in solvents of changing viscosity and dielectric permittivity. In order to establish the free energy surface (FES) of the reaction, we resort to stationary electronic spectroscopy. On the other hand, the dynamics of a non-reacting substance, Coumarin 153, provide the calibrating tool for the non-Markovian friction over the FES, which is assumed to be solute independent. A simpler and computationally faster approach uses the Generalized Smoluchowski Equation (GSE), which can be derived from the GLE for pure harmonic potentials. Both approaches reproduce the measurements in most of the solvents reasonably well. At long times, some differences arise from the errors inherited from the analysis of the stationary solvatochromism and at short times from the excess excitation energy. However, whenever the dynamics become slow, the GSE shows larger deviations than the GLE, the results of which always agree qualitatively with the measured dynamics, regardless of the solvent viscosity or dielectric properties. The method applied here can be used to predict the dynamics of any other reacting system, given the FES parameters and solvent dynamics are provided. Thus no fitting parameters enter the GLE simulations, within the applicability limits found for the model in this work.

Response surface evaluation of microwave-assisted extraction conditions for Lycium barbarum bioactive compounds

Abstract The effects of microwave-assisted extraction (MAE) on the qualitative and quantitative composition of extracted bioactive phytochemicals are strongly dependent on specific operational conditions. The impact of temperature, extraction time, and solvent dielectric properties on the MAE of antioxidant compounds from goji berry is hereby reported and discussed. Results were evaluated in terms of antioxidant capacity (ascertained by ABTS and ORAC assays), complemented with quantification of total phenolics content (TPC), and characterization of extracts through HPLC. Furthermore, the effect of storage temperature was also studied. Results revealed that temperature and solvent properties exert a significant effect on TPC and ORAC assays, whereas irradiation time plays a key role in the preparation of extracts to be evaluated through ABTS. The effect of solvent properties is tentatively explained considering the dielectric properties of methanol and water, whereas the observed effect of temperature could be explained by its influence on the solubility of phenolic compounds. Industrial Relevance A careful selection of operational conditions during MAE, designed for a specific antioxidant assay, allows an increase in the bioactivity of the resultant extracts, which may become important in terms of industrial applications.

Induced Dipole–Dipole Interactions Influence the Unfolding Pathways of Wild-Type and Mutant Amyloid β-Peptides

Amyloid-forming proteins undergo a structural transition from α-helical to disordered conformations and, ultimately, cross-β fibrils. The unfolding and aggregation of the amyloid β-peptide (Aβ) have been implicated in the development and progression of Alzheimer’s disease (AD) and cerebral amyloid angiopathy (CAA). However, the events underlying the initial structural transition leading to the disease state remain unclear. Although most cases are sporadic, several genetic variants exist that alter the electrostatic properties of Aβ and lead to more rapid unfolding and more severe phenotypes. In the present study, the enhanced unfolding is shown to be due to the mutated side chains altering the local peptide-bond dipole moments leading to local destabilization of the α-helix, as determined from polarizable molecular dynamics (MD) simulations of wild-type (WT) Aβ fragments and several common mutations. The local perturbation of the helix then leads to progressive unwinding of the α-helix in a cooperative fashion due to decreases in adjacent (i ± 1) and hydrogen-bonded (i + 4) peptide-bond dipole moments. Side-chain dynamics, subsequent variations in dipole moments, and ultimately the response in the peptide-bond dipole moments are all modulated by solvent dielectric properties based on simulations in water versus ethanol. The polarizable simulation results, along with simulations using the additive CHARMM36 force field, further indicate that cooperativity due to the alignment of peptide bonds leading to enhanced dipole moments is a fundamental force in stabilizing α-helices.

Dielectric Properties of Ethylene Carbonate and Propylene Carbonate Using Molecular Dynamics Simulations

Ethylene carbonate (EC) and propylene carbonate (PC) are two widely used solvents in Li-ion batteries and supercapacitors. Ion diffusion in these solvents depends strongly on accurate predictions of solvent dielectric properties. We used all-atom molecular dynamics simulations of these pure solvents to calculate dielectric constants and dielectric relaxation times at various temperatures. The dielectric constant measures polarization of a material whereas dielectric relaxation measures the lag of the polarization in a dielectric medium in responding to a change in an applied field. Predicted values are compared with the available experimental results to validate the force field parameters (OPLS-AA) for these solvents. Current results for dielectric constant and dielectric relaxation time indicate that OPLS-AA force field produces reasonable agreement with experiment for both EC and PC. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U. S. Department of Energys National Nuclear Security Administration under contract DE-AC04-94AL85000

Limiting equivalent electrical conductivity of inorganic salt solutions and dielectric properties of a polar solvent

A relation has been found to exist between the limiting equivalent electrical conductivity of inorganic salt solutions, viscosity, temperature, and dielectric properties of the solvent. As temperature rises, the limiting equivalent electrical conductivity of aqueous solution of an inorganic salt has been shown to increase in direct proportion to the ratio of the dielectric permittivity to the dipole dielectric relaxation time, i.e., the limiting high-frequency electrical conductivity of the polar solvent. Expressions have been derived to be used in ascertaining the limiting equivalent electrical conductivities of inorganic salt solutions proceeding from the dielectric properties of the solvent.

Dielectric properties of solvents and their limiting high-frequency conductivity

The behavior of the limiting high-frequency (HF) conductivity of water, methanol, ethanol, and propanol in a wide temperature range is considered. As the temperature is increased to its critical value, the static permittivity and the dipole relaxation time of the polar solvents decrease monotonically; however, the limiting HF conductivity, which is determined by their ratio, passes through a maximum. The maximum is explained by differences in the behavior of the temperature dependences of the relative temperature coefficients (RTCs) of static permittivity and the dipole relaxation time. It is shown that the maximum on the temperature dependence of the limiting HF conductivity corresponds to the equality of the RTCs of static permittivity and the dipole relaxation time. It is noted that in the temperature range corresponding to the maximum limiting HF conductivities of water and alcohols, the temperature dependences of the ion product of water and the conductivity of the considered polar solvents and solutions of inorganic salts in them also pass through maxima.

Microwave assisted synthesis of caffeine/maleic acid co-crystals: the role of the dielectric and physicochemical properties of the solvent

In the present work microwave radiation has been used to prepare the 1 : 1 and 2 : 1 co-crystals of caffeine and maleic acid. We obtained 1 : 1 co-crystals in the presence of water and methanol and we also see Form II of the 1 : 1 co-crystal in methanol. Co-crystallisation under microwave irradiation is shown to be controlled by the saturation of solvent at the reacting interface between the co-crystal components as well as the solvent dielectric properties.

The effect of solvent dielectric properties on the collection of oriented electrospun fibers

AbstractA simple approach to electrospinning has been developed that enables the collection of polymer, ceramic, and multiphase composite fibers, in quantity, with a high degree of spatial orientation. It has been demonstrated that a careful choice of solvent effectively eliminates the onset of the characteristic “bending” instability that is commonly associated with the electrospinning process. This allows collection of spatially oriented submicron electrospun fibers on a rotating drum without the need for elaborate mechanical or electrostatic manipulation of the electrospinning jet and/or collection target (Deitzel, J. M.; Kleinmeyer, J. D. et al. Polymer 2001, 42, 8163, Zussman, E.; Theron, A.; et al. Appl Phys Lett 2003, 82, 973, and Li, D. Wang, Y. L.; et al. Nano Lett 2003, 3, 1167). Fibers have been electrospun from a series of model polyethylene oxide/CHCl3 solutions with a range of conductivities. The experimental data confirms theoretical predictions that the onset of the bending instability is a function of the available “free” charge in the solution, which in turn is strongly influenced by the dielectric constant of the solvent. The results show that fiber orientation becomes random as the conductivity increases, indicating the need for the surface charge density to exceed a critical threshold in order for the bending instability to initiate. This method has been experimentally demonstrated with other low‐dielectric constant solvents and other common polymer, ceramic, and composite materials. Furthermore, it has been demonstrated that fibers electrospun from these solutions can be mechanically drawn to submicron dimensions (∼ 200–500 nm) by controlling drum speed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Thermal fluctuation forces and wetting layers in colloid-polymer mixtures: Derivation of an interface potential

We discuss wetting layers in phase-separated colloid-polymer mixtures adsorbed at a vertical wall, observed in recent laser scanning confocal microscopy experiments. Matching of colloid and solvent dielectric properties renders van der Waals forces negligible and provides a system governed by short-range forces and thermal fluctuations on which the subtle predictions of renormalization group (RG) theory for wetting can be tested. The width w of the fluid-fluid ("liquid-gas") interface bounding the wetting layer scales with the square root of the wetting layer thickness l, in qualitative agreement with RG theory for short-range complete wetting in three dimensions. The measured wetting layer thickness l as a function of the height h above the horizontal plane of bulk phase separation is compared with two distinct theoretical predictions. A simple heuristic interface potential V(l), first proposed in a previous report, is now fully derived, and confronted here with the interface potential based on the linear RG theory. The heuristic approach does not capture fully the RG treatment. While fundamental differences exist between the two approaches, the resulting predictions for l(h) are almost identical. However, the theory does not follow the precise shape of the experimental curve of l(h).

Role of Solvent Dielectric Properties on Charge Transfer from PbS Nanocrystals to Molecules

Transfer of photoexcited charge from PbS nanocrystals to ligand molecules is investigated in different solvents. We find that the charge transfer rate increases dramatically with solvent dielectric constant. This trend is accounted for by a modified Marcus theory that incorporates only static dielectric effects. The choice of solvent allows significant control of the charge transfer process. As an important example, we find that PbS nanocrystals dispersed in water exhibit charge transfer rates 1000 times higher than the same nanocrystals in organic solvent. Rapid charge extraction will be important to efficient nanocrystal-based photovoltaic and photodetector devices.

Dielectric permittivity and temperature effects on spin–spin couplings studied on acetonitrile

Dielectric permittivity (epsilon) and temperature effects on indirect spin-spin coupling constants were studied using acetonitrile as a probe molecule. Experiments were accompanied by hybrid DFT (density functional theory) studies, where the solvent was modeled using the polarization continuum model. Owing to its numerous types of J-couplings, acetonitrile is a very convenient molecule against which various basis sets can be tested or the best basis set can be selected for a given study. The results show reasonable agreement between calculated and experimental values. According to our data, scalar spin-spin coupling constants undergo substantial shifts at lower values of the dielectric constant. Thus J-coupling values are not transferable between measurements made at differing epsilon-conditions, and the assumption of the epsilon-independence of the J-coupling can lead to crucial mistakes in experiments using low-epsilon media. Dielectric permittivity also causes small geometric fluctuations within the molecule, which themselves can affect J-coupling values. Examinations of the results computed with frozen and relaxed geometries show that geometry mediation mostly affects the spin-dipole term of the J-coupling; hence, for accurate evaluation of the latter, frozen geometries are not acceptable. Another interesting fact revealed is the connection between the solvent dielectric properties and the temperature-dependence slopes of J-couplings in corresponding media.

On the Temperature Dependence of Amide I Frequencies of Peptides in Solution

The temperature dependence of the amide I vibrational frequencies of peptides in solution was investigated. In D2O, the amide I' bands of both an alpha-helical oligopeptide, the random-coil poly(L-lysine), and the simplest amide, N-methyl acetamide (NMA), exhibit linear frequency shifts of approximately 0.07 cm(-1)/degrees C with increasing temperature. Similar amide I frequency shifts are also observed for NMA in both polar (acetonitrile and DMSO) and nonpolar (1,4-dioxane) organic solvents, thus ruling out hydrogen-bonding strength as the cause of these effects. The experimental NMA amide I frequencies in the organic solvents can be accurately described by a simple theory based on the Onsager reaction field with temperature-dependent solvent dielectric properties and a solute molecular cavity. DFT-level calculations (BPW91/cc-pVDZ) for NMA with an Onsager reaction field confirm the significant contribution of the molecular cavity to the predicted amide I frequencies. Comparison of the computations to experimental data shows that the frequency-dependent response of the reaction field, taken into account by the index of refraction, is crucial for describing the amide I frequencies in polar solvents. The poor predictions of the model for the NMA amide I band in D2O might be due, in part, to the unknown temperature dependence of the refractive index of D2O in the mid-IR range, which was approximated by the available values in the visible region.

Synthesis and Properties of Thermosetting Modified Polyphenylene Ether

A novel method for preparing thermosetting modified Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) was developed by introducing allyl groups into PPE. It was successfully prepared from the reaction between brominated PPE and a Grignand reagent. The effects of substitution of bromine on methyl group and dosage of allylated Grignard reagent on the substitution value of allyl group were studied. The structure of the resulting allylated PPE (A-PPE) was characterized by 1H-NMR and FT-IR spectroscopy. The curing reaction process was researched by differential scanning calorimetry (DSC), and the properties of the cured A-PPE were also investigated. The curing reaction of the A-PPE was first order reaction. The curing reaction activation energy obtained by Kissinger equation was 121.7 kJ/mol. The cured A-PPE resin is excellent not only in solvent resistance and dielectric properties, but also in thermal properties, moisture absorption and adhesion with glass fiber. The dielectric constant (e) and dissipation factor (tan δ) of A-PPE composites reinforced with E-glass cloth at 1 MHz were measured as 2.84 and 2.65×10-3, respectively. In addition, A-PPE was very easy to form into films.

Solvation and intramolecular reorganization in 9,9′-bianthryl: Analysis of resonance Raman excitation profiles and ab initio molecular orbital calculations

The observations of a clear solvent-dependence of resonance Raman intensities, but an absence of concommitant changes in absorption cross-sections, are reported for the molecule 9,9′-bianthryl (BA). Displacements obtained by analysis of the nonpolar solvent data are found to reproduce the absorption spectra recorded in all solvents studied, but not the resonance Raman intensities in polar solvents. Moreover, transform theory is found to be unsuccessful in reproducing the resonance Raman intensities in any solvent. These observations suggest that ultrafast relaxation dynamics (on the timescale probed by the resonance Raman experiment) are changing the displacements of the intramolecular vibrational modes. The changes in the displacements determined by analysis of the data are consistent with a correlation between the total reorganization energy accompanying the charge transfer and the solvent dielectric properties (i.e., the mode-specific reorganization is found to increase with solvent dielectric properties). In effect, the immediate free energy surface “seen” by the molecule changes dramatically with time and causes significant intramolecular reorganization, at least for the initial stages of evolution of the emissive state. These findings are supported by ab initio molecular orbital (MO) geometry optimization, analytical frequencies, and excited state calculations (CIS/3-21G*, HF/6-31G*). It is shown that most of the normal modes of the S0 state of BA are splittings of corresponding anthracene modes, however, for the relaxed S1 geometry of BA (i.e., gas phase equilibrium geometry), the modes are calculated to be red-shifted and have significantly greater splittings. Furthermore, the dipole moment of this relaxed S1 state is calculated to be 0.099 debye in the gas phase, compared to 0.00 debye for the equilibrium ground state and the vertical, unrelaxed, S1 state. The optimized S1 geometry of BA is found to be a “90°” geometry (i.e., torsion angle between the anthracene ring planes), similar to that of the ground state except for subtle asymmetries in each anthracene ring which lower the symmetry from D2. We suggest that these results provide direct evidence for the importance of solvent-dependent intramolecular reorganization in this molecule.

Photophysical and electrochemical redox properties of fixed distance porphyrin–quinone systems

A few fixed distance covalently linked porphyrin–quinone molecules have been synthesized in which a benzoquinone is directly attached to a meso/β-pyrrole position of tri(phenyl/pentafluorophenyl)/tetraphenylporphyrins. The choice of fluoroarylporphyrins permit modulation of Δ G ET values for photoinduced electron-transfer reactions in these systems. All short distance porphyrin–quinone molecules showed efficient quenching of the porphyrin singlet excited state. The electrochemical redox data coupled with the steady-state and time-resolved singlet emission data are analysed to evaluate the dependence of Δ G ET values on the rate of electron transfer ( k ET) in these systems. The meso-trifluoroarylporphyrin–quinones are found to be sensitive probes of the surrounding dielectric environment. Varying solvent polarity on the mechanism of fluorescence quenching and k ET values revealed that short donor–acceptor distance and the solvent dielectric relaxation properties play a dominant role.