Advanced Electrostatic Model for Monovalent Ions Based on Ab Initio Energy Decomposition

Jing, Zhifeng; Liu, Chengwen; Ren, Pengyu

doi:10.1021/acs.jcim.1c00426

Cited by 11 publications

(8 citation statements)

References 47 publications

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“…More recently, significant interest has arisen with respect to the influence of polarizability on the structure and dynamics of soft matter systems. − Broadly, there are three primary methods for explicitly accounting for the effects of electronic polarization in classical simulations, namely, the induced point dipole, fluctuating charge, and the Drude oscillator models. ,, The total electrostatic energy of the induced point dipole system contains the charge–charge, charge–dipole, and dipole–dipole interactions, with the point dipole on a given atom calculated using an iterative self-consistent field (SCF) procedure. − The fluctuating charge model allows the charges on individual molecules to dynamically change according to the electronegativity of each atom in the molecule. − The Drude oscillator model attaches a ghost (Drude) particle to its host (core) particle with a harmonic spring, and then the mass and partial charge of the true atom are divided into the Drude and core portions. ,,− In general, in comparison to the traditional nonpolarizable force field (fixed charge) model, all of the polarizable models introduce additional degrees of freedom to be solved self-consistently during the simulation, which increases the computational expense and serves to explain the relatively fewer number of studies employing such a framework.…”

Section: Introductionmentioning

confidence: 99%

Influence of Polarizability on the Structure, Dynamic Characteristics, and Ion-Transport Mechanisms in Polymeric Ionic Liquids

Zhang

Zofchak

Krajniak³

et al. 2022

J. Phys. Chem. B

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We used atomistic simulations and compared the prediction of three different implementations of force fields, namely, the original full partial charge system, the scaled partial charge system, and the Drude oscillator polarizable force field and its effect on the structural and dynamic properties of a polymeric ionic liquid, poly(1-butyl-3-methyl-imidazolium hexafluorophosphate). We found that both the scaled and the polarizable force field models yield comparable predictions of structural and dynamic properties, although the scaled charge model artificially lowers the first-neighbor peak of the radial distribution function and therefore leads to a slight reduction in density. The full charge model was not accurate in its prediction of the dynamic properties but could reproduce the structural properties. With a refined analysis method for the ion-hopping mechanisms, we found that all three methods produce very similar conclusions, namely, that the mobile anion is associated with three cations from two distinct polymer chains and that the fractions of inter- and intramolecular hopping events are comparable. Our results demonstrate that the scaled charge force fields provide a computationally efficient means to capture polarizability effects on both the structural and dynamic properties of polymeric ionic liquid systems.

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Section: Introductionmentioning

confidence: 99%

Influence of Polarizability on the Structure, Dynamic Characteristics, and Ion-Transport Mechanisms in Polymeric Ionic Liquids

Zhang

Zofchak

Krajniak³

et al. 2022

J. Phys. Chem. B

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“…The scaled charge strategy by electronic continuum correction − described the electronic polarization in nonpolarizable force fields. For polarizable ion models, a different form (buffered 14-7 potential) − was adopted to represent the vdW interaction.…”

Section: Introductionmentioning

confidence: 99%

Rational Design of Nonbonded Point Charge Models for Highly Charged Metal Cations with Lennard-Jones 12-6 Potential

Zhang

Jiang

Qiu

et al. 2021

J. Chem. Inf. Model.

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Here, we developed nonbonded point charge models using a simple Lennard-Jones (LJ) 12-6 potential for highly charged metal cations (18 trivalent and 6 tetravalent ions) for use with 11 water models of TIP3P, OPC3, SPC/E, SPC/E b , TIP3P-FB, a99SB-disp, TIP4P-Ew, OPC, TIP4P/2005, TIP4P-D, and TIP4P-FB. The designed models simultaneously reproduce the hydration free energy (HFE) and ion−oxygen distance (IOD) in the first hydration shell with an error within 1 kcal/ mol and 0.01 Å on average, respectively, and yield reasonable coordination numbers for most cations. Such performance is equivalent to the previously reported point charge models using a more complex 12-6-4 LJ-type potential, while the LJ R parameters of our models are much close to Shannon's revised effective ion radii than that of the 12-6-4 models. Our designed models overestimate the diffusion constants of several trivalent ions by 5−68%. The performance in predicting osmotic coefficients of trivalent chlorides in aqueous solution depends on the salt type. A calibration of cation−anion interacting LJ parameters reproduces the experimental osmotic coefficients of an AlCl 3 solution at 0.2− 3.0 mol/L. The effectiveness of our new models is further demonstrated by simulating a metalloprotein system with four force field/ water combinations. This work facilitates accurate modeling of metal-containing systems by a variety of force fields and water models in aqueous solution.

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“…In view of this, the systematic difference of 17 kcal/mol between AMOEBA and SAPT0 + MBD values of E int in bulk water (see Table 1) is not so dissimilar from previous results. Improvements to the AMOEBA force field for ions, using SAPT energy components as benchmark data, is a topic of contemporary interest [97][98][99].…”

Section: Resultsmentioning

confidence: 99%

Interaction Energy Analysis of Monovalent Inorganic Anions in Bulk Water Versus Air/Water Interface

Herbert¹,

Paul²

2021

Molecules

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Soft anions exhibit surface activity at the air/water interface that can be probed using surface-sensitive vibrational spectroscopy, but the structural implications of this surface activity remain a matter of debate. Here, we examine the nature of anion–water interactions at the air/water interface using a combination of molecular dynamics simulations and quantum-mechanical energy decomposition analysis based on symmetry-adapted perturbation theory. Results are presented for a set of monovalent anions, including Cl−, Br−, I−, CN−, OCN−, SCN−, NO2−, NO3−, and ClOn− (n=1,2,3,4), several of which are archetypal examples of surface-active species. In all cases, we find that average anion–water interaction energies are systematically larger in bulk water although the difference (with respect to the same quantity computed in the interfacial environment) is well within the magnitude of the instantaneous fluctuations. Specifically for the surface-active species Br−(aq), I−(aq), ClO4−(aq), and SCN−(aq), and also for ClO−(aq), the charge-transfer (CT) energy is found to be larger at the interface than it is in bulk water, by an amount that is greater than the standard deviation of the fluctuations. The Cl−(aq) ion has a slightly larger CT energy at the interface, but NO3−(aq) does not; these two species are borderline cases where consensus is lacking regarding their surface activity. However, CT stabilization amounts to <20% of the total induction energy for each of the ions considered here, and CT-free polarization energies are systematically larger in bulk water in all cases. As such, the role of these effects in the surface activity of soft anions remains unclear. This analysis complements our recent work suggesting that the short-range solvation structure around these ions is scarcely different at the air/water interface from what it is in bulk water. Together, these observations suggest that changes in first-shell hydration structure around soft anions cannot explain observed surface activities.

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Advanced Electrostatic Model for Monovalent Ions Based on Ab Initio Energy Decomposition

Cited by 11 publications

References 47 publications

Influence of Polarizability on the Structure, Dynamic Characteristics, and Ion-Transport Mechanisms in Polymeric Ionic Liquids

Influence of Polarizability on the Structure, Dynamic Characteristics, and Ion-Transport Mechanisms in Polymeric Ionic Liquids

Rational Design of Nonbonded Point Charge Models for Highly Charged Metal Cations with Lennard-Jones 12-6 Potential

Interaction Energy Analysis of Monovalent Inorganic Anions in Bulk Water Versus Air/Water Interface

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