A density-functional model of the dispersion interaction

Becke, Axel D.; Johnson, Erin R.

doi:10.1063/1.2065267

Cited by 1,312 publications

(987 citation statements)

References 30 publications

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“…Grimme's D3 dispersion correction with Becke‐Johnson (BJ) damping was used to account for dispersion 61, 62, 63, 64. The 6‐311G(d,p) basis set was employed for all calculations.…”

Section: Methodsmentioning

confidence: 99%

Surface Enrichment in Equimolar Mixtures of Non‐Functionalized and Functionalized Imidazolium‐Based Ionic Liquids

et al. 2018

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For equimolar mixtures of ionic liquids with imidazolium‐based cations of very different electronic structure, we observe very pronounced surface enrichment effects by angle‐resolved X‐ray photoelectron spectroscopy (XPS). For a mixture with the same anion, that is, 1‐methyl‐3‐octylimidazolium hexafluorophosphate+1,3‐di(methoxy)imidazolium hexafluorophosphate ([C8C1Im][PF6]+[(MeO)2Im][PF6]), we find a strong enrichment of the octyl chain‐containing [C8C1Im]+ cation and a corresponding depletion of the [(MeO)2Im]+ cation in the topmost layer. For a mixture with different cations and anions, that is, [C8C1Im][Tf2N]+[(MeO)2Im][PF6], we find both surface enrichment of the [C8C1Im]+ cation and the [Tf2N]− (bis[(trifluoromethyl)sulfonyl]imide) anion, while [(MeO)2Im]+ and [PF6]− are depleted from the surface. We propose that the observed behavior in these mixtures is due to a lowering of the surface tension by the enriched components. Interestingly, we observe pronounced differences in the chemical shifts of the imidazolium ring signals of the [(MeO)2Im]+ cations as compared to the non‐functionalized cations. Calculations of the electronic structure and the intramolecular partial charge distribution of the cations contribute to interpreting these shifts for the two different cations.

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“…Grimme's D3 dispersion correction with Becke‐Johnson (BJ) damping was used to account for dispersion 61, 62, 63, 64. The 6‐311G(d,p) basis set was employed for all calculations.…”

Section: Methodsmentioning

confidence: 99%

Surface Enrichment in Equimolar Mixtures of Non‐Functionalized and Functionalized Imidazolium‐Based Ionic Liquids

et al. 2018

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“…and a 1 (2) fitted parameters for the functionals used here [44][45][46]. Note that the older -D2 correction [47,48] is a simplification (a first-version) of the above approach, which is however widely and successfully used too.…”

Section: Theoretical Detailsmentioning

confidence: 99%

Intra‐ and Intermolecular Dispersion Interactions in [n]Cycloparaphenylenes: Do They Influence Their Structural and Electronic Properties?

et al. 2015

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Cycloparaphenylenes (CPPs) are nanosized structures with challenging isolated and bulk properties. They can be also viewed as synthetic targets for the template-driven (potentially) bottom-up synthesis of carbon nanotubes. Thus, the step by step understanding of the supramolecular order at the nanoscale is of utmost relevance for further molecular engineering. We find here that intra-molecular noncovalent (dispersion) interactions must be taken into account to obtain accurate estimates of structural and optoelectronic properties of these[n]CPP compounds, analyzing also their influence as the number of repeat units increases from n = 4 up to n = 12, both in the gas phase and in solution. We also address the supramolecular self-assembly of

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“…Hirshfeld-I (HI) [11], Iterative Stockholder Analysis (ISA) [17], and a new variant of ISA. This analysis is not only relevant for for the development of improved partitioning schemes, but also for dispersion corrections in density functional theory that are based on Hirshfeld partitioning [18][19][20]. In order to obtain a smooth dispersion correction to the potential energy surface, the underlying partitioning scheme must be robust.…”

Section: Introductionmentioning

confidence: 99%

The conformational sensitivity of iterative stockholder partitioning schemes

Verstraelen¹,

Ayers²,

Speybroeck³

et al. 2012

Chemical Physics Letters

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Chemical interpretation and empirical modeling of partial charges requires a robust partitioning scheme to derive these charges from the molecular electronic density. The degree of undesirable conformational sensitivity is assessed for three iterative stockholder partitioning schemes: Hirshfeld-I (HI), Iterative Stockholder Analysis (ISA) and a new Gaussian ISA variant (GISA). GISA has fewer degrees of freedom than ISA and enforces monotonically decaying pro-atoms. These improvements accelerate the converge of GISA as compared to ISA. However, the conformational sensitivity of the charges does not decrease and is still large compared to HI.

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A density-functional model of the dispersion interaction

Cited by 1,312 publications

References 30 publications

Surface Enrichment in Equimolar Mixtures of Non‐Functionalized and Functionalized Imidazolium‐Based Ionic Liquids

Surface Enrichment in Equimolar Mixtures of Non‐Functionalized and Functionalized Imidazolium‐Based Ionic Liquids

Intra‐ and Intermolecular Dispersion Interactions in [n]Cycloparaphenylenes: Do They Influence Their Structural and Electronic Properties?

The conformational sensitivity of iterative stockholder partitioning schemes

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