The Born model can accurately describe electrostatic ion solvation

Duignan, Timothy T.; Xin, Zhao

doi:10.1039/d0cp04148c

Cited by 29 publications

(26 citation statements)

References 63 publications

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“…Indeed, it has been understood for a long time that the Born model can produce reasonable hydration energies for monatomic ions of either charge, but the requisite atomic radii are quite different for anions versus cations 46,703 . Charge hydration asymmetry therefore does not reflect a failure of continuum electrostatics per se , and is arguably better ascribed to the effects of short‐range repulsion rather than electrostatics 320,702 . This can be modeled in an ad hoc way by modifying the atomic radii based on the charge state of the atom, 704,705 but a more satisfying approach is to modify the jump boundary condition ε in E ⊥ ( s − ) = ε out E ⊥ ( s + ) in Equation (), replacing it with

([], ε_{in} - ((), ε_{out} - ε_{in}) h ((), E_{⊥}^{-})) E_{⊥} ((), {bolds}^{-}) = ([], ε_{out} - ((), ε_{out} - ε_{in}) h ((), E_{⊥}^{-})) E_{⊥} ((), {bolds}^{+}),

where

E_{⊥}^{-} \equiv E_{⊥} ((), {bolds}^{-})

.…”

Section: Anisotropic Solvationmentioning

confidence: 99%

“…As such, this model cannot describe "charge hydration asymmetry," that is, the fact that hydration energies for monovalent atomic anions are significantly larger in magnitude than those for cations. [694][695][696][697][698][699] This asymmetry, which also affects polar but charge-neutral solutes, 700 is partly attributable to water's surface potential, 701,702 however a primary origin of this effect is simply the fact that an anion sees a much different facet of a water molecule as compared to a cation, 701,702 leading to a very different electrostatic size for cations versus anions. Indeed, it has been understood for a long time that the Born model can produce reasonable hydration energies for monatomic ions of either charge, but the requisite atomic radii are quite different for anions versus cations.…”

mentioning

confidence: 99%

“…46,703 Charge hydration asymmetry therefore does not reflect a failure of continuum electrostatics per se, and is arguably better ascribed to the effects of short-range repulsion rather than electrostatics. 320,702 This can be modeled in an ad hoc way by modifying the atomic radii based on the charge state of the atom, 704,705 but a more satisfying approach is to modify the jump boundary condition ε in E ⊥ (s − ) = ε out E ⊥ (s + ) in Equation (2.22), replacing it with…”

mentioning

confidence: 99%

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Dielectric continuum methods for quantum chemistry

Herbert

2021

WIREs Comput Mol Sci

142

195

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This review describes the theory and implementation of implicit solvation models based on continuum electrostatics. Within quantum chemistry this formalism is sometimes synonymous with the polarizable continuum model, a particular boundary‐element approach to the problem defined by the Poisson or Poisson–Boltzmann equation, but that moniker belies the diversity of available methods. This work reviews the current state‐of‐the art, with emphasis on theory and methods rather than applications. The basics of continuum electrostatics are described, including the nonequilibrium polarization response upon excitation or ionization of the solute. Nonelectrostatic interactions, which must be included in the model in order to obtain accurate solvation energies, are also described. Numerical techniques for implementing the equations are discussed, including linear‐scaling algorithms that can be used in classical or mixed quantum/classical biomolecular electrostatics calculations. Anisotropic models that can describe interfacial solvation are briefly described. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Molecular and Statistical Mechanics > Free Energy Methods

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([], ε_{in} - ((), ε_{out} - ε_{in}) h ((), E_{⊥}^{-})) E_{⊥} ((), {bolds}^{-}) = ([], ε_{out} - ((), ε_{out} - ε_{in}) h ((), E_{⊥}^{-})) E_{⊥} ((), {bolds}^{+}),

where

E_{⊥}^{-} \equiv E_{⊥} ((), {bolds}^{-})

.…”

Section: Anisotropic Solvationmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Dielectric continuum methods for quantum chemistry

Herbert

2021

WIREs Comput Mol Sci

142

195

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“…51,56,57 Specifically, the reduced polarizability of confined water molecules lessens the free solvation energy of the ion and hence its overall hydration capacity. 39,58,59 It is thus reasonable that the formation of hydrates with h I + ≥ 4 would be unfavorable in low-dielectric environments. Our results also indicate that sodium monohydrates, (H 2 O)Na + , became the dominant species after filtering 10 mM NaCl through Trisep 3 (Figure S7c), with the proportion of each larger hydrate sequentially decreasing (i.e., χ n=1 > χ n=2 > χ n=3 ).…”

Section: Dehydration Of Sodium Ions During Transmembranementioning

confidence: 99%

In Situ Characterization of Dehydration during Ion Transport in Polymeric Nanochannels

Ritt

et al. 2021

J. Am. Chem. Soc.

122

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The transport of hydrated ions across nanochannels is central to biological systems and membrane-based applications, yet little is known about their hydrated structure during transport due to the absence of in situ characterization techniques. Herein, we report experimentally resolved ion dehydration during transmembrane transport using modified in situ liquid ToF-SIMS in combination with MD simulations for a mechanistic reasoning. Notably, complete dehydration was not necessary for transport to occur across membranes with sub-nanometer pores. Partial shedding of water molecules from ion solvation shells, observed as a decrease in the average hydration number, allowed the alkali-metal ions studied here (lithium, sodium, and potassium) to permeate membranes with pores smaller than their solvated size. We find that ions generally cannot hold more than two water molecules during this sterically limited transport. In nanopores larger than the size of the solvation shell, we show that ionic mobility governs the ion hydration number distribution. Viscous effects, such as interactions with carboxyl groups inside the membrane, preferentially hinder the transport of the mono-and dihydrates. Our novel technique for studying ion solvation in situ represents a significant technological leap for the nanofluidics field and may enable important advances in ion separation, biosensing, and battery applications.

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“…The Born model provides a good approximation to the magnitude of the charging free energies, although the simulated free energies display a slight asymmetry with respect to Q. This asymmetry is becoming increasingly well understood, and arises from the asymmetric charge distribution of the molecular model [81][82][83][84]93 , in addition to the asymmetric nature of the solute-solvent excluded volume interactions 94,95 .…”

Section: Free Energy Of Hard Sphere Charging In Liquid Methanementioning

confidence: 99%

Distributed Charge Models of Liquid Methane and Ethane for Dielectric Effects and Solvation

Thakur,

Remsing

2020

Preprint

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Liquid hydrocarbons are often modeled with fixed, symmetric, atom-centered charge distributions and Lennard-Jones interaction potentials that reproduce many properties of the bulk liquid. While useful for a wide variety of applications, such models cannot capture dielectric effects important in solvation, selfassembly, and reactivity. The dielectric constants of hydrocarbons, such as methane and ethane, physically arise from electronic polarization fluctuations induced by the fluctuating liquid environment. In this work, we present non-polarizable, fixed-charge models of methane and ethane that break the charge symmetry of the molecule to create fixed molecular dipoles, the fluctuations of which reproduce the experimental dielectric constant. These models can be considered a mean-field-like approximation that can be used to include dielectric effects in large-scale molecular simulations of polar and charged molecules in liquid methane and ethane. We further demonstrate that solvation of model solutes in these fixed-dipole models improve upon dipole-free models.

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The Born model can accurately describe electrostatic ion solvation

Abstract: Accurate models of the free energies of ions in solution are crucially important. They can be used to predict and understand the properties of electrolyte solutions in the huge number...

Cited by 29 publications

References 63 publications

Dielectric continuum methods for quantum chemistry

Dielectric continuum methods for quantum chemistry

In Situ Characterization of Dehydration during Ion Transport in Polymeric Nanochannels

Distributed Charge Models of Liquid Methane and Ethane for Dielectric Effects and Solvation

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