Static permittivity of water revisited: ε in the electric field above 10<sup>8</sup>V m<sup>−1</sup>and in the temperature range 273 ≤ T ≤ 373 K

Danielewicz-Ferchmin, I.; Ferchmin, A. R.

doi:10.1039/b314337f

Cited by 31 publications

(34 citation statements)

References 29 publications

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“…This linearity is consistent with the fact that the mean cosine values remain well below unity. The absence of saturation is not unexpected, because although dielectric saturation occurs at high electric fields, such as at the surface of ions, 69,70 little saturation is expected in the lower electric fields near the neutral polar solutes studied here.…”

Section: Resultsmentioning

confidence: 97%

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

Muddana

Sapra

Fenley

et al. 2013

The Journal of Chemical Physics

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Continuum solvation models are widely used to estimate the hydration free energies of small molecules and proteins, in applications ranging from drug design to protein engineering, and most such models are based on the approximation of a linear dielectric response by the solvent. We used explicit-water molecular dynamics simulations with the TIP3P water model to probe this linear response approximation in the case of neutral polar molecules, using miniature cucurbituril and cyclodextrin receptors and protein side-chain analogs as model systems. We observe supralinear electrostatic solvent responses, and this nonlinearity is found to result primarily from waters' being drawn closer and closer to the solutes with increased solute-solvent electrostatic interactions; i.e., from solute electrostriction. Dielectric saturation and changes in the water-water hydrogen bonding network, on the other hand, play little role. Thus, accounting for solute electrostriction may be a productive approach to improving the accuracy of continuum solvation models. © 2013 AIP Publishing LLC.

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Section: Resultsmentioning

confidence: 97%

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

Muddana

Sapra

Fenley

et al. 2013

The Journal of Chemical Physics

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“…and the effective relative dielectric constant at the radius of the hydration shell is estimated to be 12 « 3. 16 The change in the Coulomb potential energy is then calculated to be ¹17 « 3 kJ mol ¹1 , in fair agreement with ¦G = ¹8.0 kJ mol ¹1 for sodium halide aqueous solutions and negatively charged SiOH groups. 17 We consider the siloxane bond sites in a similar way.…”

Section: ¹2mentioning

confidence: 64%

“…18 From the dipole moment (0.24 D), the effective charge of silyl groups in disiloxane molecules is calculated to be +0.050 e, with the oxygen atom having a charge of ¹0.10 e. When the siloxane site and adsorbed ion are both hydrated, the effective relative permittivities are calculated to be approximately 75 around a siloxane bond and 4045 around a cation. 16 Using these values, the change in Coulomb potential energy was calculated to be ¹0.36 kJ mol…”

Section: ¹2mentioning

confidence: 99%

On the Relation between the Interfacial Charge of a Discharging Nozzle and Electrification of a Liquid Microjet

Kurahashi

Suzuki

2018

Chem. Lett.

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A liquid microjet discharged from a fused silica capillary is electrified, and the polarity of this electrification is opposite to that of the net charge at the solidliquid interface of the capillary nozzle. Keywords: Liquid microjet | Fused silica | Capillary nozzleLiquid microjets, cylindrical streams of liquid with a diameter of tens of micrometers, are now widely employed in photoelectron spectroscopy of liquids 1 and gas-surface scattering experiments.2 The small surface area of the microjet minimizes evaporation of solvent molecules and facilitates introduction of volatile liquids into high-vacuum chambers. However, a liquid microjet is electrically charged, because the liquid flow shears off an electric double layer at the inner wall of a capillary nozzle to create unequal number densities of cations and anions in the mobile part of the flow (flow electrification). 3,4 In a previous study, 5 we showed that the electric potential of a liquid microjet of NaX solution (X = Cl, Br, and I) varies with the electrolyte concentration. A notable common feature of the variation was that the polarity of the potential reverses at around a concentration of 30 mM (Figure 1), suggesting that Na + plays a key role in determining the polarity. In the present work, we discuss the relation between the electric charge at the inner wall of a capillary and the microjet.The electric potential (º d ) in the diffuse region of an electric double layer is described by the PoissonBoltzmann equation as follows,where e is the elementary charge, ¾ 0 and ¾ r are respectively the permittivity of vacuum and the relative permittivity of a solution, Z « and N « are respectively the charge and number density of positive/negative ions, k B is the Boltzmann constant, and T is the temperature. Equation 1 cannot be solved analytically. However, if the electric potential is sufficiently small such that the following condition holds, i.e.,an approximate solution can be expressed aswhere l is the distance from the inner wall of the capillary, º OHP is the electric potential at the outer Helmholtz plane (OHP), and l OHP is the position of the OHP. ¬ is the inverse of the Debye length, defined aswhere c is the concentration of the solution. º OHP is related to the interfacial charge º 0 bywhere · surf is the original charge density of the solid surface, · ad is the charge density of the adsorbed ions, and l IHP is the position of the inner Helmholtz plane (IHP). The relative permittivity is assumed to be the same in all regions of the solution. Then, the continuity conditions for the electric field and the potential at the OHP yieldIf eq 2 holds, the charge density in the diffuse layer is given bySince Z þ ¼ 1 and Z À ¼ À1 for NaX, eq 7 simplifies to μðlÞ % À2ceº OHP e À¬ðlÀlOHPÞ ð8ÞThis equation shows that the excess charge in a diffuse layer is opposite in sign to both º OHP and · surf þ · ad . Although eq 3 is valid only for small º d , the opposite signs of μ and · surf þ · ad are expected to be general. In this study, we examine the relation bet...

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“…The permittivity e = eA C H T U N G T R E N N U N G (s,P,T) has been taken from refs. [15,16,25]. Since the actual dependence of the volume V = V(P) on the local electrostriction pressure P is not available, the isotherms V = V(P) of H 2 O under external pressure P in the absence of a field [26] are applied instead.…”

Section: Rigorous Equation Of State Of H 2 O Expressed In Terms Of Tmentioning

confidence: 99%

“…[13,14] The strength of the local field is % 10 9 V m À1 and for such field values the water permittivity is e < 35. [15,16] [a] Prof. A. R. ) are found for six different experimental lines of the N-D transition found in the literature. The values s D correspond to the crossings of the total pressure (P t + P) vs s isotherms at different T t (PÀelectrostriction pressure).…”

Section: Introductionmentioning

confidence: 99%

Properties of Hydration Shells of Protein Molecules at their Pressure‐ and Temperature‐Induced Native‐Denatured Transition

Danielewicz-Ferchmin¹,

Banachowicz²,

Ferchmin³

2006

ChemPhysChem

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Properties of water at the surface of biomolecules are important for their conformational stability. The behaviour of hydrating water at protein transition (t) pressures P(t) and temperatures T(t) , with the points (P(t),T(t) ) lying in the Native-Denatured (N-D) transition line, is studied. Hydration shells at the hydrophilic regions of protein molecules with surface charge density sigma are investigated with the help of the equation of state of water in an open system. The local values of sigma rather close to each other (sigma(D) approximately 0.3 C m(-2)) are found for six different experimental lines of the N-D transition found in the literature. The values sigma(D) correspond to the crossings of the total pressure (P(t)+Pi) vs sigma isotherms at different T(t) (Pi-electrostriction pressure). The pressures P(t) and temperatures T(t) appear to be related with some selected sites at the surfaces of the protein molecules.

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Static permittivity of water revisited: ε in the electric field above 10⁸V m⁻¹and in the temperature range 273 ≤ T ≤ 373 K

Cited by 31 publications

References 29 publications

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

On the Relation between the Interfacial Charge of a Discharging Nozzle and Electrification of a Liquid Microjet

Properties of Hydration Shells of Protein Molecules at their Pressure‐ and Temperature‐Induced Native‐Denatured Transition

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Static permittivity of water revisited: ε in the electric field above 108V m−1and in the temperature range 273 ≤ T ≤ 373 K

Cited by 31 publications

References 29 publications

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

The electrostatic response of water to neutral polar solutes: Implications for continuum solvent modeling

On the Relation between the Interfacial Charge of a Discharging Nozzle and Electrification of a Liquid Microjet

Properties of Hydration Shells of Protein Molecules at their Pressure‐ and Temperature‐Induced Native‐Denatured Transition

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Static permittivity of water revisited: ε in the electric field above 10⁸V m⁻¹and in the temperature range 273 ≤ T ≤ 373 K