Charge neutrality breakdown in confined aqueous electrolytes: Theory and simulation

Colla, Thiago; Girotto, Matheus; Santos, Alexandre Pereira dos; Levin, Yan

doi:10.1063/1.4962198

Cited by 49 publications

(57 citation statements)

References 123 publications

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“…The traditional Poisson-Boltzmann (PB) theory is recovered when both size and electrostatic correlations are neglected [34] (µ cor i = µ hs i = 0). For computing these contributions beyond the mean-field level, we shall here invoke a second-order bulk functional expansion approximation for the electrostatic correlations [80,[93][94][95], while describing finite size effects in the framework of the accurate Fundamental Measure Theory (FMT).…”

Section: Density Functional Theorymentioning

confidence: 99%

“…which is quite accurate up to very high electrostatic couplings of the underlying bulk electrolyte [80]. The pair interactions u ij (r) comprise both excluded volume and the electrostatic interactions.…”

Section: Density Functional Theorymentioning

confidence: 99%

“…To this end, a Density Functional Theory (DFT) is applied which allows one to accurately account for the ionic osmotic equilibrium across an infinitely thin spherical charged surface that represents a coarse grained description of an icosahedral, quasi-spherical, shell. The applied DFT accurately incorporates size and electrostatic correlations into the calculation of ionic free energies [80]. We then combine the results of the DFT with a continuum model of shell elasticity, allowing us to calculate the osmotic stresses across the interface and the equilibrium shell size.…”

Section: Introductionmentioning

confidence: 99%

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Osmotic stress and pore nucleation in charged biological nanoshells and capsids

2020

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A model system is proposed to investigate the chemical equilibrium and mechanical stability of biological spherical-like nanoshells in contact with an aqueous solution with added dissociated electrolyte of a given concentration. The ionic chemical equilibrium across the permeable shell is investigated in the framework of an accurate Density Functional Theory (DFT) that incorporates electrostatic and hardcore correlations beyond the traditional mean-field (e. g., Poisson-Boltzmann) limit. The accuracy of the theory is tested by a direct comparison with Monte Carlo (MC) simulations. A simple analytical expression is then deduced which clearly highlights the entropic, electrostatic, and self-energy contributions to the osmotic stress over the shell in terms of the calculated ionic profiles. By invoking a continuum mean-field elastic approach to account for the shell surface stress upon osmotic stretching, the mechanical equilibrium properties of the shell under a wide variety of ionic strengths and surface charges are investigated. The model is further coupled to a continuum mechanical approach similar in structure to a Classical Nucleation Theory (CNT) to address the question of mechanical stability of the shells against a pore nucleation. This allows us to construct a phase diagram which delimits the mechanical stability of capsids for different ionic strengths and shell surface charges. * Electronic address: colla@ufop.edu.br † Electronic address: amin.bakhshandeh@ufrgs.br ‡ Electronic address: levin@if.ufrgs.br

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Section: Density Functional Theorymentioning

confidence: 99%

Section: Density Functional Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Osmotic stress and pore nucleation in charged biological nanoshells and capsids

2020

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“…This is due to appearance of special functions in the two dimensional Fourier transform, leading to slow convergence of the lattice sums [9][10][11] . This notwithstanding, there are many important systems with a broken symmetry: ionic liquids at electrified interfaces [12][13][14][15][16][17] , charged nanopores [18][19][20] , nanoconfined electrolytes [21][22][23] , just to cite a handful of examples. These systems can present new phenomena, such as like-charged attraction [24][25][26][27] and charge reversal [28][29][30] , which are hard to describe analytically 31 , hence the importance of fast simulation methods.…”

Section: Introductionmentioning

confidence: 99%

Simulations of Coulomb systems confined by polarizable surfaces using periodic Green functions

Santos

Girotto

Levin

2017

The Journal of Chemical Physics

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We present an efficient approach for simulating Coulomb systems confined by planar polarizable surfaces. The method is based on the solution of the Poisson equation using periodic Green functions. It is shown that the electrostatic energy arising from the surface polarization can be decoupled from the energy due to the direct Coulomb interaction between the ions. This allows us to combine an efficient Ewald summation method, or any other fast method for summing over the replicas, with the polarization contribution calculated using Green function techniques. We apply the method to calculate density profiles of ions confined between the charged dielectric and metal surfaces.

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“…Recalling that ρ ± Appendix C: Derivation of Eq. (38) We recall the expression of the electroosmotic flow…”

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confidence: 99%

Driving an electrolyte through a corrugated nanopore

Malgaretti

Janssen

Pagonabarraga

et al. 2019

The Journal of Chemical Physics

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We characterize the dynamics of a z − z electrolyte embedded in a varying-section channel. In the linear response regime, by means of suitable approximations, we derive the Onsager matrix associated to externally enforced gradients in electrostatic potential, chemical potential, and pressure, for both dielectric and conducting channel walls. We show here that the linear transport coefficients are particularly sensitive to the geometry and the conductive properties of the channel walls when the Debye length is comparable to the channel width.In this regime, we found that one pair of off-diagonal Onsager matrix elements increases with the corrugation of the channel transport, in contrast to all other elements which are either unaffected by or decrease with increasing corrugation. Our results have a possible impact on the design of blue-energy devices as well as on the understanding of biological ion channels through membranes

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Charge neutrality breakdown in confined aqueous electrolytes: Theory and simulation

Cited by 49 publications

References 123 publications

Osmotic stress and pore nucleation in charged biological nanoshells and capsids

Osmotic stress and pore nucleation in charged biological nanoshells and capsids

Simulations of Coulomb systems confined by polarizable surfaces using periodic Green functions

Driving an electrolyte through a corrugated nanopore

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