A reduced radial potential energy function for the halogen bond and the hydrogen bond in complexes B⋯XY and B⋯HX, where X and Y are halogen atoms

Legon, A. C.

doi:10.1039/c4cp01444h

Cited by 50 publications

(63 citation statements)

References 92 publications

(29 reference statements)

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“…The full geometries of these complexes are available in the form of the cartesian coordinates in the Supplementary Material. We note from Tables 1 and 2 Tables 1 and 2, that these complexes tend to be more strongly bound according to both criteria (D e and k σ ) than those of a wide range of hydrogen-, halogen-, tetrel-, pnictogen-and chalcogen-bonded complexes with a similar set of Lewis bases previously investigated [20][21][22]. Typically, for the hydrogen-and halogen-bonded complexes considered in [22] Table 2.…”

Section: Molecular Geometriesmentioning

confidence: 80%

“…We note from Tables 1 and 2 Tables 1 and 2, that these complexes tend to be more strongly bound according to both criteria (D e and k σ ) than those of a wide range of hydrogen-, halogen-, tetrel-, pnictogen-and chalcogen-bonded complexes with a similar set of Lewis bases previously investigated [20][21][22]. Typically, for the hydrogen-and halogen-bonded complexes considered in [22] Table 2. It should be noted, from Table 1 and Table 2, that these complexes tend to be more strongly bound according to both criteria (De and kσ) than those of a wide range of hydrogen-, halogen-, tetrel-, pnictogen-and chalcogen-bonded complexes with a similar set of Lewis bases previously investigated [20][21][22].…”

Section: Molecular Geometriesmentioning

confidence: 80%

“…The first is the energy required to remove the component molecules from the hypothetical equilibrium separation to infinite distance, while the second is a measure of the work required for a unit infinitesimal displacement from the equilibrium. It has been shown [20][21][22] that for a wide range of hydrogen-, halogen-, tetrel-, pnictogen-and chalcogen-bonded complexes, D e is directly proportional to k σ and, moreover, that it is possible to reproduce the D e values (and, therefore, the k σ values also) by assigning a set of electrophilicities, E A , to the Lewis acids, A, and nucleophilicities, N B , to the Lewis bases, B. An important aim of the present article is to discover whether this partitioning also applies to beryllium-and magnesium-bonded complexes.…”

Section: Introductionmentioning

confidence: 99%

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Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)

Alkorta

Legon

2019

Inorganics

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Geometries, equilibrium dissociation energies (De), intermolecular stretching, and quadratic force constants (kσ) determined by ab initio calculations conducted at the CCSD(T)/aug-cc-pVTZ level of theory, with De obtained by using the complete basis set (CBS) extrapolation [CCSD(T)/CBS energy], are presented for the B···BeR2 and B···MgR2 complexes, where B is one of the following Lewis bases: CO, H2S, PH3, HCN, H2O or NH3, and R is H, F or CH3. The BeR2 and MgR2 precursor molecules were shown to be linear and non-dipolar. The non-covalent intermolecular bond in the B···BeR2 complexes is shown to result from the interaction of the electrophilic band around the Be atom of BeR2 (as indicated by the molecular electrostatic potential surface) with non-bonding electron pairs of the base, B, and may be described as a beryllium bond by analogy with complexes such as B···CO2, which contain a tetrel bond. The conclusions for the B···MgR2 series are similar and a magnesium bond can be correspondingly invoked. The geometries established for B···BeR2 and B···MgR2 can be rationalized by a simple rule previously enunciated for tetrel-bonded complexes of the type B···CO2. It is also shown that the dissociation energy, De, is directly proportional to the force constant, kσ, in each B···MR2 series, but with a constant of proportionality different from that established for many hydrogen-bonded B···HX complexes and halogen-bonded B···XY complexes. The values of the electrophilicity, EA, determined from the De for B···BeR2 complexes for the individual Lewis acids, A, reveal the order A = BeF2 > BeH2 > Be(CH3)2—a result that is consistent with the −I and +I effects of F and CH3 relative to H. The conclusions for the MgR2 series are similar but, for a given R, they have smaller electrophilicities than those of the BeR2 series. A definition of alkaline-earth non-covalent bonds is presented.

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Section: Molecular Geometriesmentioning

confidence: 80%

Section: Molecular Geometriesmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 99%

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Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)

Alkorta

Legon

2019

Inorganics

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“…It had been shown that many hydrogen-and halogen-bonded complexes have binding energies directly proportional to the intermolecular stretching force constant and that both could therefore reasonably be described by the Morse potential. 18 The Lennard-Jones 19,20 potential which can be regarded as a special case of the Mie potential, 21 is the common choice for describing intermolecular interactions (such as van der Waals interactions, hydrogen bonding, and halogen bonding). The Lennard-Jones function offers computational advantages over other functions and it has only two adjustable parameters.…”

Section: Potential Energy Functionsmentioning

confidence: 99%

Is there any fundamental difference between ionic, covalent, and others types of bond? A canonical perspective on the question

Walton

Rivera‐Rivera

Lucchese

et al. 2017

Phys. Chem. Chem. Phys.

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The concept of chemical bonding is normally presented and simplified through two models: the covalent bond and the ionic bond. Expansion of the ideal covalent and ionic models leads chemists to the concepts of electronegativity and polarizability, and thus to the classification of polar and non-polar bonds. In addition, the intermolecular interactions are normally viewed as physical phenomena without direct correlation to the chemical bond in any simplistic model. Contrary to these traditional concepts of chemical bonding, recently developed canonical approaches demonstrate a unified perspective on the nature of binding in pairwise interatomic interactions. This new canonical model, which is a force-based approach with a basis in fundamental molecular quantum mechanics, confirms much earlier assertions that in fact there are no fundamental distinctions among covalent bonds, ionic bonds, and intermolecular interactions including the hydrogen bond, the halogen bond, and van der Waals interactions.

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“…Tests of this model showed remarkably small deviations from experiment of less than 0.5 kcal mol −1 in many cases, although unsurprisingly these errors increased upon extrapolation to new systems. More recent work has attempted to extend this approach to other types of non-covalent interaction, including halogen bonds [68,69]. Such a model would be ideal for halogen-bonded systems as it requires minimal effort.…”

Section: Introductionmentioning

confidence: 99%

A Simple Model for Halogen Bond Interaction Energies

Shaw

Hill

2019

Inorganics

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Halogen bonds are prevalent in many areas of chemistry, physics, and biology. We present a statistical model for the interaction energies of halogen-bonded systems at equilibrium based on high-accuracy ab initio benchmark calculations for a range of complexes. Remarkably, the resulting model requires only two fitted parameters, X and B—one for each molecule—and optionally the equilibrium separation, R e , between them, taking the simple form E = X B / R e n . For n = 4 , it gives negligible root-mean-squared deviations of 0.14 and 0.28 kcal mol - 1 over separate fitting and validation data sets of 60 and 74 systems, respectively. The simple model is shown to outperform some of the best density functionals for non-covalent interactions, once parameters are available, at essentially zero computational cost. Additionally, we demonstrate how it can be transferred to completely new, much larger complexes and still achieve accuracy within 0.5 kcal mol - 1 . Using a principal component analysis and symmetry-adapted perturbation theory, we further show how the model can be used to predict the physical nature of a halogen bond, providing an efficient way to gain insight into the behavior of halogen-bonded systems. This means that the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction.

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A reduced radial potential energy function for the halogen bond and the hydrogen bond in complexes B⋯XY and B⋯HX, where X and Y are halogen atoms

Cited by 50 publications

References 92 publications

Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)

Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)

Is there any fundamental difference between ionic, covalent, and others types of bond? A canonical perspective on the question

A Simple Model for Halogen Bond Interaction Energies

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