Noncapillary-Wave Structure at the Water-Alkane Interface

Mitrinovic, Dragoslav M.; Tikhonov, A. M.; Li, Ming; Huang, Zheng-Qing; Schlossman, Mark L.

doi:10.1103/physrevlett.85.582

Cited by 226 publications

(220 citation statements)

References 23 publications

Supporting

Mentioning

188

Contrasting

Unclassified

Order By: Relevance

“…1B. The fitted values of roughness (4.2 → 4.9 Å) for all fits of the PB/MD model are within 2 SDs (i.e., within ± 0:4 Å) of the values calculated from capillary wave theory using our interfacial tension measurements (10,21) (Table S1). …”

Section: Resultsmentioning

confidence: 69%

Tuning ion correlations at an electrified soft interface

Laanait

Mihaylov

Hou

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

101

View full text Add to dashboard Cite

Ion distributions play a central role in various settings-from biology, where they mediate the electrostatic interactions between charged biomolecules in solution, to energy storage devices, where they influence the charging properties of supercapacitors. These distributions are determined by interactions dictated by the chemical properties of the ions and their environment as well as the long-range nature of the electrostatic force. Recent theoretical and computational studies have explored the role of correlations between ions, which have been suggested to underlie a number of counterintuitive results, such as like-charge attraction. However, the interdependency between ion correlations and other interactions that ions experience in solution complicates the connection between physical models of ion correlations and the experimental investigation of ion distributions. We exploit the properties of the liquid/liquid interface to vary the coupling strength Γ of ion-ion correlations from weak to strong while monitoring their influence on ion distributions at the nanometer scale with X-ray reflectivity and the macroscopic scale with interfacial tension measurements. These data are in agreement with the predictions of a parameterfree density functional theory that includes ion-ion correlations and ion-solvent interactions over the entire range of experimentally tunable correlation coupling strengths (from 0.8 to 3.7). This study provides evidence for a sharply defined electrical double layer for large coupling strengths in contrast to the diffuse distributions predicted by mean field theory, thereby confirming a common prediction of many ion correlation models. The reported findings represent a significant advance in elucidating the nature and role of ion correlations in charged soft matter.liquid surface scattering | ion density profile | surface excess charge | Poisson-Boltzmann | Debye-Hückel hole T he works by Gouy (1) and Chapman (2) introduced the Poisson-Boltzmann (PB) equation to describe the distribution of ions and the accompanying variation of electric potential at the interface between a charged planar electrode and an electrolyte solution (1, 2). This seminal theory considered point-like ions interacting through their mean electric field in a continuum solvent but neglected both chemically specific ion-solvent interactions and correlations between ions. Specific ion interactions are exemplified by the well-known Hofmeister series (3). The study of ion correlations has been motivated by observations of the reentrant condensation of DNA (4) and proteins (5) in solution, in which like-charged biomolecules aggregate in the presence of multivalent ions, and reports of charge reversal in colloidal suspensions, in which the sign of the screened charge on a colloid can be changed by varying the surrounding electrolyte solution (6, 7).Correlations between ions that are caused by their electrostatic interactions are expected to be important when the average electrostatic interaction energy between neighboring ions...

show abstract

Section: Resultsmentioning

confidence: 69%

Tuning ion correlations at an electrified soft interface

Laanait

Mihaylov

Hou

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

101

View full text Add to dashboard Cite

show abstract

“…The possibility of such a phase transition at an alkanewater interface has been discussed for a long time [3,4,5,6,7]. The observation of a solid -liquid phase transition at the n-hexane -water interface in the Gibbs monolayer of a surfactant is reported in this work.…”

mentioning

confidence: 63%

Solid–liquid phase transition in a Gibbs monolayer of melissic acid at the n-hexane–water interface

Tikhonov

2015

Jetp Lett.

View full text Add to dashboard Cite

show abstract

“…However, several theoretical and experimental studies have demonstrated the existence of a smooth intrinsic density profile with a finite width [25][26][27][28][29][30]44 .…”

Section: Interfacial Tensionmentioning

confidence: 99%

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Jorge

Cordeiro

2008

J. Phys. Chem. B

View full text Add to dashboard Cite

We present results of molecular dynamics simulations of the interface between water and 2-nitrophenyloctyl ether (NPOE). This system is analyzed in detail using a procedure to calculate intrinsic profiles of several important properties (density, radial distribution functions, hydrogen bonds, molecular orientation, self-diffusion). The interface was found to be molecularly sharp, but corrugated by thermal fluctuations. Using a method based on capillary wave theory, we have estimated the interfacial tension and obtained good agreement with values calculated from the virial route. The results were compared to simulations of the water/nitrobenzene interface. The presence of an alkyl chain in NPOE introduces an added degree of hydrophobicity, which causes an increase in the interfacial tension. Furthermore, interfacial NPOE molecules are less organized than nitrobenzene and show a distinct dynamic response. These results shed light on the observed differences between these two organic liquids in electrochemical studies.

show abstract

Noncapillary-Wave Structure at the Water-Alkane Interface

Cited by 226 publications

References 23 publications

Tuning ion correlations at an electrified soft interface

Tuning ion correlations at an electrified soft interface

Solid–liquid phase transition in a Gibbs monolayer of melissic acid at the n-hexane–water interface

Molecular Dynamics Study of the Interface between Water and 2-Nitrophenyl Octyl Ether

Contact Info

Product

Resources

About