Microscopic formulation of non-local electrostatics in polar liquids embedding polarizable ions

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Microscopic formulation of non-local electrostatics in polar liquids embedding polarizable ions. / Buyukdagli, Sahin; Ala-Nissilä, Tapio.

In: Physical Review E, Vol. 87, No. 6, 063201, 2013, p. 1-14.

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@article{c8c35338788b4163b544c2f4c5bf71a0,
title = "Microscopic formulation of non-local electrostatics in polar liquids embedding polarizable ions",
abstract = "Nonlocal electrostatic interactions associated with finite solvent size and ion polarizability are investigated within the mean-field linear response theory. To this end, we introduce a field-theoretic model of a polar liquid composed of linear multipole solvent molecules and embedding polarizable ions modeled as Drude oscillators. Unlike previous dipolar Poisson-Boltzmann formulations treating the solvent molecules as point dipoles, our model is able to qualitatively reproduce the non-local dielectric response behavior of polar liquids observed in molecular dynamics simulations and atomic force microscope experiments for water solvent at charged interfaces. The present theory explains the formation of the associated interfacial hydration layers in terms of a cooperative dipolar response mechanism driven by the reaction of the solvent molecules to their own polarization field. We also incorporate into the theory the relative multipole moments of water molecules obtained from quantum mechanical calculations and show that the multipolar contributions to the dielectric permittivity are largely dominated by the dipolar one. We find that this stems from the mutual cancellation of the first two interfacial hydration layers of opposite net charge for multipolar liquids. Within the same nonlocal dielectric response theory, we show that the induced ion polarizability reverses the interfacial ion density trends predicted by the Poisson-Boltzmann theory, resulting in a surface affinity of coions and exclusion of counterions. The results indicate that the consideration of the discrete charge composition of solvent molecules and ions is the key step towards a microscopic understanding of nonlocal electrostatic effects in polar solvents.",
keywords = "Polar liquid, non-local electrostatics, ion polarizability, Polar liquid, non-local electrostatics, ion polarizability, Polar liquid, non-local electrostatics, ion polarizability",
author = "Sahin Buyukdagli and Tapio Ala-Nissil{\"a}",
year = "2013",
doi = "10.1103/PhysRevE.87.063201",
language = "English",
volume = "87",
pages = "1--14",
journal = "Physical Review E",
issn = "2470-0045",
publisher = "American Physical Society",
number = "6",

}

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TY - JOUR

T1 - Microscopic formulation of non-local electrostatics in polar liquids embedding polarizable ions

AU - Buyukdagli, Sahin

AU - Ala-Nissilä, Tapio

PY - 2013

Y1 - 2013

N2 - Nonlocal electrostatic interactions associated with finite solvent size and ion polarizability are investigated within the mean-field linear response theory. To this end, we introduce a field-theoretic model of a polar liquid composed of linear multipole solvent molecules and embedding polarizable ions modeled as Drude oscillators. Unlike previous dipolar Poisson-Boltzmann formulations treating the solvent molecules as point dipoles, our model is able to qualitatively reproduce the non-local dielectric response behavior of polar liquids observed in molecular dynamics simulations and atomic force microscope experiments for water solvent at charged interfaces. The present theory explains the formation of the associated interfacial hydration layers in terms of a cooperative dipolar response mechanism driven by the reaction of the solvent molecules to their own polarization field. We also incorporate into the theory the relative multipole moments of water molecules obtained from quantum mechanical calculations and show that the multipolar contributions to the dielectric permittivity are largely dominated by the dipolar one. We find that this stems from the mutual cancellation of the first two interfacial hydration layers of opposite net charge for multipolar liquids. Within the same nonlocal dielectric response theory, we show that the induced ion polarizability reverses the interfacial ion density trends predicted by the Poisson-Boltzmann theory, resulting in a surface affinity of coions and exclusion of counterions. The results indicate that the consideration of the discrete charge composition of solvent molecules and ions is the key step towards a microscopic understanding of nonlocal electrostatic effects in polar solvents.

AB - Nonlocal electrostatic interactions associated with finite solvent size and ion polarizability are investigated within the mean-field linear response theory. To this end, we introduce a field-theoretic model of a polar liquid composed of linear multipole solvent molecules and embedding polarizable ions modeled as Drude oscillators. Unlike previous dipolar Poisson-Boltzmann formulations treating the solvent molecules as point dipoles, our model is able to qualitatively reproduce the non-local dielectric response behavior of polar liquids observed in molecular dynamics simulations and atomic force microscope experiments for water solvent at charged interfaces. The present theory explains the formation of the associated interfacial hydration layers in terms of a cooperative dipolar response mechanism driven by the reaction of the solvent molecules to their own polarization field. We also incorporate into the theory the relative multipole moments of water molecules obtained from quantum mechanical calculations and show that the multipolar contributions to the dielectric permittivity are largely dominated by the dipolar one. We find that this stems from the mutual cancellation of the first two interfacial hydration layers of opposite net charge for multipolar liquids. Within the same nonlocal dielectric response theory, we show that the induced ion polarizability reverses the interfacial ion density trends predicted by the Poisson-Boltzmann theory, resulting in a surface affinity of coions and exclusion of counterions. The results indicate that the consideration of the discrete charge composition of solvent molecules and ions is the key step towards a microscopic understanding of nonlocal electrostatic effects in polar solvents.

KW - Polar liquid, non-local electrostatics, ion polarizability

KW - Polar liquid, non-local electrostatics, ion polarizability

KW - Polar liquid

KW - non-local electrostatics

KW - ion polarizability

UR - http://pre.aps.org/abstract/PRE/v87/i6/e063201

U2 - 10.1103/PhysRevE.87.063201

DO - 10.1103/PhysRevE.87.063201

M3 - Article

VL - 87

SP - 1

EP - 14

JO - Physical Review E

JF - Physical Review E

SN - 2470-0045

IS - 6

M1 - 063201

ER -

ID: 822194