A model with charges and polarizability for CS2 in an ionic liquid

Lynden‐Bell, R. M.; Stone, Anthony J.

doi:10.1007/s12039-017-1243-0

Cited by 8 publications

(7 citation statements)

References 21 publications

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“…For instance, Stasyuk and coworkers [104], as well as several others [195], have recently proposed new models for evaluating charges that could be utilized for arriving at a fundamental understanding of some chemical systems, including endohedral fullerenes. Evidently, atomic charge is certainly a valuable property [196] that will continue to play a crucial role in the understanding systems in diverse areas of science.…”

Section: Is the Concept Of Atomic Charge Meaningful?mentioning

confidence: 99%

“…We note further that the sulfur quadrupole moment in CS 2 is positive and, and, there is negative π-electron density around the S atom but a positive σ-hole along the axis. The carbon quadrupole moment is negative, reflecting a reduced π-electron density around the C atom [196]. Because of this nature of the molecule, Singh et al [281] found that the molecule displays versatile coordination modes, and has ability to feature crossed, parallel-stacked, T-shaped, and L-shaped geometries in its clusters.…”

Section: Examples Of Some Crystalmentioning

confidence: 99%

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Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site.

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Section: Is the Concept Of Atomic Charge Meaningful?mentioning

confidence: 99%

Section: Examples Of Some Crystalmentioning

confidence: 99%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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“…Figure 3 shows the electrostatic field around a CS 2 molecule (left) and the difference between this and two point charge models (centre and right). The centre figure shows the result from the best model with charges on the three sites, while the right hand figure shows the improvement obtained by adding additional charges on either side of the S sites making a 7-site model [21]. However this is a case where the polarisability may be important and site polarisabilities were calculated with Misquitta and Stone's CamCASP program [22].…”

Section: Csmentioning

confidence: 99%

“…Due to symmetry the average electric field must be zero at each site, although there are fluctuations in its value. In the [dmim][NTf 2 ] and [bmim][NTF 2 ] solutions we found that the root mean square (rms) value of the field components at each site was 0.13pm0.02V/ Å perpendicular to the axis and 0.24±0.02V/ Å along the axis [21]. The fields tend to be largest along the molecular axes.…”

Section: Csmentioning

confidence: 99%

Lennard–Jones Lecture 2017^*

Lynden‐Bell

2018

Molecular Physics

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Some examples of the use of Molecular Dynamics Simulation to study solutions of small molecules in ionic liquids are discussed. It is shown that electrostatic forces, while not the dominant solute-solvent interaction, determine the local solute environment. The solubility of aromatics and the changes in the spectra of low frequency intermolecular vibrations in two related ionic liquids (one dicationic and one monocationic) are compared with experimental results and related to the local environment.

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“…Aim of this work was to further optimize the force field of Pádua et al to better represent dynamical properties like selfdiffusion coefficients, reorientational correlation times, and viscosities. As shown in their original work from 2007 as well as in further works published by different groups, the KPL force field has been proven to yield reliable results for dynamical properties, but also thermodynamical properties, such as the free energies of solvation for light gases in ionic liquids [17,18], and is still used frequently to this date [19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Revisiting Imidazolium Based Ionic Liquids: Effect of the Conformation Bias of the [NTf$_{2}$] Anion Studied By Molecular Dynamics Simulations

Golub¹,

Neumann²,

Odebrecht³

et al. 2017

Preprint

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We study ionic liquids composed 1-alkyl-3-methylimidazolium cations and bis(trifluoromethylsulfonyl)imide anions ([CnMIm][NTf2]) with varying chain-length n = 2, 4, 6, 8 by using molecular dynamics simulations. We show that a reparametrization of the dihedral potentials as well as charges of the [NTf2] anion leads to an improvment of the force field model introduced by Köddermann et al. [ChemPhysChem, 8, 2464[ChemPhysChem, 8, (2007] (KPL-force field). A crucial advantage of the new parameter set is that the minimum energy conformations of the anion (trans and gauche), as deduced from ab initio calculations and Raman experiments, are now both well represented by our model. In addition, the results for [CnMIm][NTf2] show that this modification leads to an even better agreement between experiment and molecular dynamics simulation as demonstrated for densities, diffusion coefficients, vaporization enthalpies, reorientational correlation times, and viscosities. Even though we focused on a better representation of the anion conformation, also the alkyl chain-length dependence of the cation behaves closer to the experiment. We strongly encourage to use the new NGKPL force field for the [NTf2] anion instead of the earlier KPL parameter set for computer simulations aiming to describe the thermodynamics, dynamics and also structure of imidazolium based ionic liquids.

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A model with charges and polarizability for CS2 in an ionic liquid

Cited by 8 publications

References 21 publications

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Lennard–Jones Lecture 2017^*

Revisiting Imidazolium Based Ionic Liquids: Effect of the Conformation Bias of the [NTf$_{2}$] Anion Studied By Molecular Dynamics Simulations

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A model with charges and polarizability for CS2 in an ionic liquid

Cited by 8 publications

References 21 publications

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Lennard–Jones Lecture 2017*

Revisiting Imidazolium Based Ionic Liquids: Effect of the Conformation Bias of the [NTf$_{2}$] Anion Studied By Molecular Dynamics Simulations

Contact Info

Product

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Lennard–Jones Lecture 2017^*