The osmotic coefficient of rod-like polyelectrolytes: Computer simulation, analytical theory, and experiment

Deserno, Markus; Holm, Christian; Blaul, Jürgen; Ballauff, Matthias; Rehahn, Matthias

doi:10.1007/s101890170091

Cited by 51 publications

(64 citation statements)

References 43 publications

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“…[7], we report the prediction of classical Oosawa-Manning condensation theory (see e.g. [19,52]), for which the osmotic coefficient is constant [φ = ℓ DN A /(2ℓ B )] at complete variance with the experiments. In view of the results reported in Fig.…”

Section: Osmotic Properties Of Rod-like Polyionsmentioning

confidence: 87%

“…This is a general feature that neglect of ionic correlation (as in PB) leads to a underestimated screening of the macro-ion by the micro-ions, and thus to overestimated effective charges (see e.g. [52,56] in cylindrical geometry). Our approach thus provides a useful upper limit for a realistic Z eff .…”

Section: Discussion -Validity Of the Approachmentioning

confidence: 99%

“…In this work, the authors measured the osmotic coefficient φ = Π osm /Π c , defined as the ratio between the osmotic pressure Π osm to the pressure Π c of releasable counter-ions having bare density c c (Π c = k B T c c ) against the concentration of B-DNA, a rigid cylindrical polyelectrolyte. A related PB cell analysis may be found in [48] while a more thorough investigation has been performed in [52].…”

Section: Osmotic Properties Of Rod-like Polyionsmentioning

confidence: 99%

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Effective charge saturation in colloidal suspensions

Bocquet

Trizac

Aubouy

2002

The Journal of Chemical Physics

141

182

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Because micro-ions accumulate around highly charged colloidal particles in electrolyte solutions, the relevant parameter to compute their interactions is not the bare charge, but an effective (or renormalized) quantity, whose value is sensitive to the geometry of the colloid, the temperature or the presence of added-salt. This non-linear screening effect is a central feature in the field of colloidal suspensions or polyelectrolyte solutions. We propose a simple method to predict effective charges of highly charged macro-ions, that is reliable for mono-valent electrolytes (and counter-ions) in the colloidal limit (large size compared to both screening length and Bjerrum length). Taking reference to the non linear Poisson-Boltzmann theory, the method is successfully tested against the geometry of the macro-ions, the possible confinement in a Wigner-Seitz cell, and the presence of added salt. Moreover, our results are corroborated by various experimental measures reported in the literature. This approach provides a useful route to incorporate the non-linear effects of charge renormalization within a linear theory for systems where electrostatic interactions play an important role.

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Section: Osmotic Properties Of Rod-like Polyionsmentioning

confidence: 87%

Section: Discussion -Validity Of the Approachmentioning

confidence: 99%

Section: Osmotic Properties Of Rod-like Polyionsmentioning

confidence: 99%

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Effective charge saturation in colloidal suspensions

Bocquet

Trizac

Aubouy

2002

The Journal of Chemical Physics

141

182

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“…The fraction of condensed counterions has been examined both in theory 16,17 and in experiments. 18,19 Counterion condensation and fluctuations have been…”

Section: Introductionmentioning

confidence: 99%

Soft effective interactions between weakly charged polyelectrolyte chains

Konieczny

Likos

Löwen

2004

The Journal of Chemical Physics

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We apply extensive Molecular Dynamics simulations and analytical considerations in order to study the conformations and the effective interactions between weakly charged, flexible polyelectrolyte chains in salt-free conditions. We focus on charging fractions lying below 20%, for which case there is no Manning condensation of counterions and the latter can be thus partitioned in two states: those that are trapped within the region of the flexible chain and the ones that are free in the solution. We examine the partition of counterions in these two states, the chain sizes and the monomer distributions for various chain lengths, finding that the monomer density follows a Gaussian shape. We calculate the effective interaction between the centers of mass of two interacting chains, under the assumption that the chains can be modeled as two overlapping Gaussian charge profiles. The analytical calculations are compared with measurements from Molecular Dynamics simulations. Good quantitative agreement is found for charging fractions below 10%, where the chains assume coil-like configurations, whereas deviations develop for charge fraction of 20%, in which case a conformational transition of the chain towards a rodlike configuration starts to take place.

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“…In the framework of the cell model, the system osmotic pressure π is equal to the thermal energy k B T times counterion concentration at the cell boundary, B cell ( ) k Tn R   [2,9,19]. The predictions of the cell model for counterion density profile and system pressure were tested by Holm et al [20][21][22]. They have shown that the cell model overestimates the system pressure even in the case of the monovalent ions for sufficiently strong electrostatic coupling.…”

Section: Introductionmentioning

confidence: 99%

Salt Effect on Osmotic Pressure of Polyelectrolyte Solutions: Simulation Study

Carrillo

Dobrynin

2014

Polymers

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Abstract:We present results of the hybrid Monte Carlo/molecular dynamics simulations of the osmotic pressure of salt solutions of polyelectrolytes. In our simulations, we used a coarse-grained representation of polyelectrolyte chains, counterions and salt ions. During simulation runs, we alternate Monte Carlo and molecular dynamics simulation steps. Monte Carlo steps were used to perform small ion exchange between simulation box containing salt ions (salt reservoir) and simulation box with polyelectrolyte chains, counterions and salt ions (polyelectrolyte solution). This allowed us to model Donnan equilibrium and partitioning of salt and counterions across membrane impermeable to polyelectrolyte chains. Our simulations have shown that the main contribution to the system osmotic pressure is due to salt ions and osmotically active counterions. The fraction of the condensed (osmotically inactive) counterions first increases with decreases in the solution ionic strength then it saturates. The reduced value of the system osmotic coefficient is a universal function of the ratio of the concentration of osmotically active counterions and salt concentration in salt reservoir. Simulation results are in a very good agreement with osmotic pressure measurements in sodium polystyrene sulfonate, DNA, polyacrylic acid, sodium polyanetholesulfonic acid, polyvinylbenzoic acid, and polydiallyldimethylammonium chloride solutions.

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The osmotic coefficient of rod-like polyelectrolytes: Computer simulation, analytical theory, and experiment

Cited by 51 publications

References 43 publications

Effective charge saturation in colloidal suspensions

Effective charge saturation in colloidal suspensions

Soft effective interactions between weakly charged polyelectrolyte chains

Salt Effect on Osmotic Pressure of Polyelectrolyte Solutions: Simulation Study

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