Does electron density in bond critical point reflect the formal charge distribution in H-bridges? The case of charge-assisted hydrogen bonds (CAHBs)

Bankiewicz, Barbara; Palusiak, Marcin

doi:10.1016/j.comptc.2011.02.021

Cited by 32 publications

(34 citation statements)

References 79 publications

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“…Again, the electron density measured at H-BCP depends on the distance between atoms forming H-bond, but does not seem to depend on the formal charge distribution within H-bridges. (Our previous work 78 showed that the concept of formal charges in H-bridges and the results of population analysis made within the framework of QTAIM are in agreement with each other.) See Figure 1 for graphical representation of data under discussion.…”

Section: And N + -H Br the E Ind Component Is The Largest At D H Asupporting

confidence: 72%

“…Recently some of us reported that the properties of electron density expressed as a function of distance do not depend on the formal charge distribution in a given H-bridge. 78 The same relationship between electron density in H-BCP and distance was observed for both non-CAHB and CAHB(+/À). Therefore, for the given distance electron density in H-BCP was practically the same for both neutral and CAHBs, despite the fact that the difference in interaction energy was larger than a hundred of kcal/mol.…”

Section: And N + -H Br the E Ind Component Is The Largest At D H Asupporting

confidence: 71%

“…Similarly to earlier paper, 78 we estimate here the electron density properties at H-BCPs as a function of the distance. This gives us a unique possibility to compare in a conclusive way the QTAIM-based parameters of electron density function measured in BCP of CAHBs of different type.…”

Section: ' Introductionmentioning

confidence: 97%

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Electron Density Characteristics in Bond Critical Point (QTAIM) versus Interaction Energy Components (SAPT): The Case of Charge-Assisted Hydrogen Bonding

2011

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Charge-assisted hydrogen bonds (CAHBs) of N-H···Cl, N-H···Br, and P-H···Cl type were investigated using advanced computational approach (MP2/aug-cc-pVTZ level of theory). The properties of electron density function defined in the framework of Quantum Theory of Atoms in Molecules (QTAIM) were estimated as a function of distance in H-bridges. Additionally, the interaction energy decomposition was performed for H-bonded complexes with different H-bond lengths using the Symmetry-Adapted Perturbation Theory (SAPT). In this way both QTAIM parameters and SAPT energy components could be expressed as a function of the same variable, that is, the distance in H-bridge. A detailed analysis of the changes in QTAIM and SAPT parameters due to the changes in H···A distance revealed that, over some ranges of H···A distances, electrostatic, inductive and dispersive components of the SAPT interaction energy show a linear correlation with the value of the electron density at H-BCP ρ(BCP). The linear relation between the induction component, E(ind), and ρ(BCP) confirms numerically the intuitive expectation that the ρ(BCP) reflects directly the effects connected with the sharing of electron density between interacting centers. These conclusions are important in view of charge density studies performed for crystals in which the distance between atoms results not only from effects connected with the interaction between atomic centers directly involved in bonding, but also from packing effects which may strongly influence the length of the H-bond.

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Section: And N + -H Br the E Ind Component Is The Largest At D H Asupporting

confidence: 72%

Section: And N + -H Br the E Ind Component Is The Largest At D H Asupporting

confidence: 71%

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Electron Density Characteristics in Bond Critical Point (QTAIM) versus Interaction Energy Components (SAPT): The Case of Charge-Assisted Hydrogen Bonding

2011

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“…It was also demonstrated that the strength of the given chemical bond is related to the amount of electron density in BCP (q BCP ). This observation was made for both shared bonds [45][46][47][48][49][50] and the bonds of closed-shell character [51][52][53][54][55] (Note that some exceptions were also reported [56][57][58]). There are also other parameters of electron density function in BCP, which may give valuable information on the bonding, such as the laplacian of electron density, r 2 qBCP, and its components being the eigenvalues of hessian in BCP 2 .…”

Section: Resultsmentioning

confidence: 97%

EL: the new aromaticity measure based on one-electron density function

Dominikowska

Palusiak

2012

Struct Chem

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Ellipticity of the bond, being the quantity which numerically reflects how far the given chemical bond has elliptic cross-section, may be used to estimate p-electron contribution in bonding. We make use of that fact and develop a new measure of aromaticity-EL index. Since ellipticity is available from calculations on oneelectron density function, EL can be used for both theoretical and experimental data. The EL measure is normalized to make interpretation of this parameter as easy and comfortable as possible. We compare EL values with the values of other commonly used aromaticity measures, such as HOMA, PDI, FLU, and NICS. It appears that the indications of EL are in agreement with indications of other indices and general expectations.

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“…Therefore, the QTAIM analysis confirmed the predictions made on the basis of the X-ray structural properties that the intramolecular N7-H7…O1 contact can be classified as a strong hydrogen bond, especially when compared with the binding energy of hydrogen bonds in water dimer, which is about 4-5 kcal/mol [42]. As already mentioned, the investigated hydrogen bond can be classified as a charge-assisted one and it has been demonstrated Struct Chem (2014) 25:979-989 985 recently that for this type of interactions the energy obtained from QTAIM analysis may be underestimated due to the fact that electrostatic interactions are not reflected directly by the charge distribution [43,44]. Thus, it is possible that the N7-H7…O1 contact is in fact much stronger than it could result from a direct relation between V H-BCP and E int .…”

Section: Intramolecular Hydrogen Bondmentioning

confidence: 99%

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

et al. 2014

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X-ray analysis of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide reveals the temperature-dependent polymorphism associated with the crystallographic symmetry conversion. The observed crystal structure transformation corresponds to a symmetry reduction from I4 1 /a (I) to P4 3 (II) space groups. The phase transition mainly concerns the subtle but clearly noticeable reorganization of molecules in the crystal space, with the structure of individual molecules left almost unchanged. The Hirshfeld surface analysis shows that various intermolecular contacts play an important role in the crystal packing, revealing graphically the differences in spatial arrangements of the molecules in both polymorphs. The N-oxide oxygen atom acts as a formally negatively charged hydrogen bonding acceptor in intramolecular hydrogen bond of N-H…O -type. The combined crystallographic and theoretical DFT methods demonstrate that the observed intramolecular N-oxide N-H…O hydrogen bond should be classified as a very strong charge-assisted and closed-shell non-covalent interaction.

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Does electron density in bond critical point reflect the formal charge distribution in H-bridges? The case of charge-assisted hydrogen bonds (CAHBs)

Cited by 32 publications

References 79 publications

Electron Density Characteristics in Bond Critical Point (QTAIM) versus Interaction Energy Components (SAPT): The Case of Charge-Assisted Hydrogen Bonding

Electron Density Characteristics in Bond Critical Point (QTAIM) versus Interaction Energy Components (SAPT): The Case of Charge-Assisted Hydrogen Bonding

EL: the new aromaticity measure based on one-electron density function

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

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