The electrostatic potential at atomic sites as a reactivity index in the hydrogen bond formation

Galabov, Boris; Bobadova‐Parvanova, Petia; Ilieva, Sylvia; Dimitrova, Valia

doi:10.1016/s0166-1280(03)00149-0

Cited by 55 publications

(61 citation statements)

References 31 publications

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“…In this context, Galebov and coworkers emphasized the usefulness of the EPN as a hydrogen bonding reactivity index. 37 Platts has also shown that EPN correlates accurately with the hydrogen bond donor capacity. 38 …”

Section: Electrostatic Forces and Epnmentioning

confidence: 97%

Advances in electric field and atomic surface derived properties from experimental electron densities

Bouhmaida

Ghermani

2008

Phys. Chem. Chem. Phys.

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The present study is devoted to a general use of the Gauss law. This is applied to the atomic surfaces derived from the topological analysis of the electron density. The method proposed here is entirely numerical, robust and does not necessitate any specific parametrization of the atomic surfaces. We focus on two fundamental properties: the atomic charges and the electrostatic forces acting on atoms in molecules. Application is made on experimental electron densities modelized by the Hansen-Coppens model from which the electric field is derived for a heterogenic set of compounds: water molecule, NO(3) anion, bis-triazine molecule and MgO cluster. Charges and electrostatic forces are estimated by the atomic surface flux of the electric field and the Maxwell stress tensor, respectively. The charges obtained from the present method are in good agreement with those issued from the conventional volume integration. Both Feynman and Ehrenfest forces as well as the electrostatic potential at the nuclei (EPN) are here estimated from the experimental electron densities. The values found for the molecular compounds are presented and discussed in the scope of the mechanics of atomic interactions.

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Section: Electrostatic Forces and Epnmentioning

confidence: 97%

Advances in electric field and atomic surface derived properties from experimental electron densities

Bouhmaida

Ghermani

2008

Phys. Chem. Chem. Phys.

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“…At a first approximation, and even if a merely qualitative discussion in terms of Mulliken charges could result insufficient to illustrate the question 11, 53–56, the calculated changes in the charge distribution over the CN bond are similar in all the complexes studied here: there is a drastic reduction of the Δ q , expressed as the difference between the C charge (always +) and the N charge (always −), just opposite that observed in the O(N)H bond, where the participation of the H atom in HB increases Δ q (i.e. “ionizes” the bond) and lengthens the O(N)H distance.…”

Section: Resultsmentioning

confidence: 79%

Vibrational dynamics of hydrogen‐bonded HCN complexes with OH and NH acids: Computational DFT systematic study

Alía

Edwards

2006

Int J of Quantum Chemistry

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Vibrational properties (band position, infrared [IR], and Raman intensities)of C'N stretching mode were studied in 65 gas phase hydrogen-bonded 1:1 complexes of HCN with OH acids and NH acids using density functional theory (DFT) calculations at the B3LYP-6-311ϩϩG(d,p) level. Furthermore, general characteristics of the hydrogen bonds and vibrational changes in acids OH/NH stretching bands were also considered. Experimentally observed blue shift of the C'N stretching band promoted by hydrogen bonding, which shortens the triple bond length, is very well reproduced and quantitatively depends on the hydrogen bond length. Both IR and Raman (C'N) band intensities are enhanced, also in good agreement with the experimental results. IR intensity increase is a direct function of the hydrogen bond energy. However, the predicted Raman intensity raise is a more complex function, depending simultaneously on characteristics of both the hydrogen bond (C'N bond length) and the H-donating acid (polarizability). With these two parameters, (C'N) Raman intensities of the complexes are explained with a mean error of Ϯ2.4%.

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“…The transferred charge is but one parameter that correlates well with the HB energy. Other such factors include potential on the hydrogen of isolated donor 18, 32, proton affinities of the components 7, 33–35, magnetic resonance shielding constants and inter‐ and intramolecular spin–spin coupling constants 36, increments of vibrational frequencies 31, 32, 36, shift of proton from donor to acceptor, and the effect of elongation of the proton donating bond resulting from the HB formation 17, 29. Finally, we ought to mention the most thoroughly investigated, topological properties of electron density, its curvatures, and its Laplacian at the HB b.c.p.…”

Section: Resultsmentioning

confidence: 99%

“…This time the sets differed in acceptors, NH 3 or H 2 O. The set of complexes with the NH 3 acceptor was previously used by Galabov in the study of the electrostatic potential at atomic sites as a reactivity index in the HB formation 18.…”

Section: Introductionmentioning

confidence: 99%

Transfer of electron density as a result of hydrogen bond formation

Sadlej-Sosnowska

2008

Int J of Quantum Chemistry

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It has been found that the amount of charge transfer between donor and acceptor molecules in four sets of hydrogen-bonded complexes may be adequately described as an exponential function of the equilibrium distance between the hydrogen atom and the nearest atom of the acceptor molecule. The exponential factors of the transfer are of the same order but somewhat larger than the factors found otherwise in the investigations of dynamic electron transfer.

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The electrostatic potential at atomic sites as a reactivity index in the hydrogen bond formation

Cited by 55 publications

References 31 publications

Advances in electric field and atomic surface derived properties from experimental electron densities

Advances in electric field and atomic surface derived properties from experimental electron densities

Vibrational dynamics of hydrogen‐bonded HCN complexes with OH and NH acids: Computational DFT systematic study

Transfer of electron density as a result of hydrogen bond formation

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