Unravelling the solvent response to neutral and charged solutes

Fedorov, Maxim V.; Kornyshev, Alexei A.

doi:10.1080/00268970601110316

Cited by 101 publications

(122 citation statements)

References 91 publications

(127 reference statements)

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“…26,27,51,65 However, since ε W (z) is not a monotonic but oscillating function of depth z, displaying both positive and negative values separated by sharp discontinuities within 0.5 nm of the interface, 29,[66][67][68] interfacial ion distributions should not be expected to be monotonic or even continuous functions of depth. 66 From this standpoint, relative ion affinities would reflect the dissimilar depths, z i , at which ions balance the electrodynamic forces driving them to the interface with the entropic losses associated with the creation of interfacial concentration gradients.…”

Section: Resultsmentioning

confidence: 99%

Hofmeister effects in micromolar electrolyte solutions

Enami

Mishra

Hoffmann

et al. 2012

The Journal of Chemical Physics

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Ions induce both specific (Hofmeister) and non-specific (Coulomb) effects at aqueous interfaces. More than a century after their discovery, the origin of specific ion effects (SIE) still eludes explanation because the causal electrostatic and non-electrostatic interactions are neither local nor separable. Since direct Coulomb effects essentially vanish below ∼10 μM (i.e., at >50 nm average ion separations in water), we decided to investigate whether SIE operate at, hitherto unexplored, lower concentrations. Herein, we report the detection of SIE above ∼0.1 μM in experiments where relative iodide/bromide populations, χ = I − /Br − , were determined on the surface of aqueous (NaI + NaBr) jets by online electrospray mass spectrometry in the presence of variable XCl (X = H, Na, K, Cs, NH 4 , and N(C 4 H 9 ) 4 ) and NaY (Y = OH, Cl, NO 3 , and ClO 4 ) concentrations. We found that (1) all tested electrolytes begin to affect χ below ∼1 μM and (2) I − and Br − are preferentially suppressed by co-ions closely matching their interfacial affinities. We infer that these phenomena, by falling outside the reach of even the longest ranged electrostatic interactions, are dynamical in nature.

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Section: Resultsmentioning

confidence: 99%

Hofmeister effects in micromolar electrolyte solutions

Enami

Mishra

Hoffmann

et al. 2012

The Journal of Chemical Physics

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“…4 This procedure presents some clear conceptual difficulties, but, from the practical perspective, has also run into problems when applied to molecular-size objects 22,43 and to nanometer-scale liquid interfaces. 17,34 The deviations from the expected behavior are not limited to quantitative disagreements in calculated electrostatic energies, but reach the level of qualitative differences.…”

Section: Discussionmentioning

confidence: 99%

Electrostatics of liquid interfaces

Matyushov

2014

The Journal of Chemical Physics

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The standard Maxwell formulation of the problem of polarized dielectrics suffers from a number of difficulties, both conceptual and practical. These difficulties are particularly significant in the case of liquid interfaces, where the ability of the interfacial multipoles to change their orientations to minimize their free energies leads to interfacial polarization localized within a thin microscopic layer. A formalism to capture this physical reality of localized interfacial polarization is proposed and is based on the surface charge as the source of microscopic electric fields in dielectrics. The surface charge density incorporates the local structure of the interface into electrostatic calculations. The corresponding surface susceptibility and interface dielectric constant provide local closures to the electrostatic boundary value problem. A robust approach to calculate the surface susceptibility from numerical simulations is proposed. The susceptibility can alternatively be extracted from a number of solution experiments, in particular those sensitive to the overall dipole moment of a closed dielectric surface. The theory is applied to the solvent-induced spectral shift and high-frequency dielectric response of solutions.

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“…This technique is easy to implement but it suffers from poor convergence. 143,221,239 The more advanced methods that are most commonly used to solve OZ-type equations can be roughly classified into four general domains. In the first category there are methods based on…”

Section: 143238mentioning

confidence: 99%

“…This effect arises by indirect coupling of the correlations with solvent molecules since the ion-solvent and ion-ion interaction potentials are not altered a priori. The XRISM, ARISM, and DRISM methods have been used to study aqueous ionic solutions in both the infinite dilution regime 137,171,187,213,[217][218][219][220][221] and over a range of finite salt concentrations. 175,215,[222][223][224][225][226][227][228][229] These studies have used a number of different water and ion models at both ambient conditions 141,221 and at extreme temperatures, 225,226,228,229 pressures, 228,229 and concentrations.…”

Section: D Rismmentioning

confidence: 99%