Density Functional Studies of the bπ.aσ Charge-Transfer Complex Formed between Ethyne and Chlorine Monofluoride

García, Antón; Cruz, Elso Manuel Cruz; Sarasola, C.; Ugalde, Jesús M.

doi:10.1021/jp9628646

Cited by 18 publications

(23 citation statements)

References 29 publications

(44 reference statements)

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“…However, for charge-transfer complexes large differences in the equilibrium geometry can be expected for different methods. In particular, hybrid XC functionals are able to produce equilibrium structures very close to the reference ones but semilocal XC approximations lead to significantly shorter intermolecular distances [50][51][52]54]. As shown in Ref.…”

Section: Role Of Geometrymentioning

confidence: 99%

Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes

Laricchia

Fabiano

Sala

2013

The Journal of Chemical Physics

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We apply the frozen density embedding method, using a full relaxation of embedded densities through a freeze-and-thaw procedure, to study the electronic structure of several benchmark ground-state charge-transfer complexes, in order to assess the merits and limitations of the approach for this class of systems. The calculations are performed using both semilocal and hybrid exchange-correlation (XC) functionals. The results show that embedding calculations using semilocal XC functionals yield rather large deviations with respect to the corresponding supermolecular calculations. Due to a large error cancellation effect, however, they can often provide a relatively good description of the electronic structure of charge-transfer complexes, in contrast to supermolecular calculations performed at the same level of theory. On the contrary, when hybrid XC functionals are employed, both embedding and supermolecular calculations agree very well with each other and with the reference benchmark results. In conclusion, for the study of ground-state charge-transfer complexes via embedding calculations hybrid XC functionals are the method of choice due to their higher reliability and superior performance.

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Section: Role Of Geometrymentioning

confidence: 99%

Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes

Laricchia

Fabiano

Sala

2013

The Journal of Chemical Physics

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“…Some of the complexes presented herein (Table 1) have been analyzed in previous studies. These are the FCl···NH 3 , [44][45][46][47][48][49][50][51][52] FBr···NH 3 , [52] SeFH···NH 3 , [53,54] PFH 2 ···NH 3 , [55] SFH···C 2 H 2 , [56] FCl···C 2 H 2 , [46][47][48][57][58][59] PFH 2 ···C 2 H 2 , [60] and Si/GeFH 3 ···NH 3 [61,62] complexes. However,c alculations were performed at different levels and these studies concerned rather narrow types of interaction;h erein the same high level of calculation was applied for the varioust ypes of s-hole bond.…”

Section: Lewisa Cidmentioning

confidence: 99%

Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Grabowski

Sokalski

2017

ChemPhysChem

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Representative Lewis acid-Lewis base complexes linked by tetrel, pnicogen, chalcogen, and halogen bonds have been studied within the quantum theory of atoms in molecules (QTAIM) approach and the hybrid variation-perturbation theory (HVPT) to analyze possible relationships between these σ-hole dimers. Results obtained at the MP2/aug-cc-pVTZ level indicate numerous correlations similar to hydrogen-bonded systems.

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“…The halogen bond has been computationally characterized by the interaction of a region of positive electrostatic potential on the halogen atoms, known as the σ-hole, with the negative electrostatic potential of a Lewis base [13][14][15][16]. A large number of different Lewis bases have been used to form such complexes [11], including carbenes [17,18], boron derivatives [19][20][21][22], σ-bonds [23,24] and π-systems [25,26]. As with the hydrogen bond, the effects of cooperativity [27,28] in the clusters formed by halogen bonds or in connection with other noncovalent bonds have been observed [29][30][31][32][33].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

2020

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A theoretical study of the hydrogen bond (HB) and halogen bond (XB) complexes between 1-halo-closo-carboranes and hydrogen cyanide (NCH) as HB and XB probe has been carried out at the MP2 computational level. The energy results show that the HB complexes are more stable than the XBs for the same system, with the exception of the isoenergetic iodine derivatives. The analysis of the electron density with the quantum theory of atoms in molecules (QTAIM) shows the presence of a unique intermolecular bond critical point with the typical features of weak noncovalent interactions (small values of the electron density and positive Laplacian and total energy density). The natural energy decomposition analysis (NEDA) of the complexes shows that the HB and XB complexes are dominated by the charge-transfer and polarization terms, respectively. The work has been complemented with a search in the CSD database of analogous complexes and the comparison of the results, with those of the 1-halobenzene:NCH complexes showing smaller binding energies and larger intermolecular distances as compared to the 1-halo-closo-carboranes:NCH complexes.

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Density Functional Studies of the bπ.aσ Charge-Transfer Complex Formed between Ethyne and Chlorine Monofluoride

Cited by 18 publications

References 29 publications

Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes

Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes

Are Various σ‐Hole Bonds Steered by the Same Mechanisms?

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

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