Bond indices in dihydrogen bonds

Giambiagi, Myriam M. S. de; Bultinck, Patrick

doi:10.1590/s0103-50532008000200009

Cited by 4 publications

(3 citation statements)

References 43 publications

(60 reference statements)

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“…In this form the C3−C5 bond length increases from 1.45 (S1) to 1.59 Å (S2), and the O2−O3 bond was also found to be longer, 1.49 Å, compared to 1.22 Å for 1 O 2 molecule. The weakness of these bonds upon the oxygen adsorption is confirmed by analyzing the Wiberg bond index (Wbi), which decreases from 1.18 (C3−C5 in S1) and 2.02 (O−O, molecular oxygen) to 0.89 and 0.98 in the S2 structure, respectively. It is also interesting to notice that the O 2 is chemically bound to the tube surface, with the Wbi factor found to be 0.85 for C3−O2 and C5−O3 (S2 structure), characterizing a single bond.…”

Section: Resultsmentioning

confidence: 95%

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

et al. 2009

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In order to understand the morphology of oxidized positions in single-wall carbon nanotubes (SWNTs), several chemical models, resulting from the interaction of an armchair (5,5) carbon nanotube (a(5,5)) with molecular oxygen and water, have been proposed. Structural and thermodynamic properties were calculated using the density functional theory at the B3LYP/6-31G(d) level, and the results are discussed with an aim to assess the viability of the processes and structures proposed. In addition, the changes in the Raman active modes relative to the D and G absorption regions were analyzed and the characteristic frequencies assigned. In general, our results show a blue shift of about 10 cm -1 in the D band with the progress of the oxidation reaction and an opposite trend for the G band, which is red-shifted by about 5 cm -1 . Although the extension of oxidation was short as reported in the present paper, taking only 1 mol of O 2 and water, the main functional groups were generated: CdO, C-O-C, and C-OH. Thus, the analysis described here can be valuable for experimentalists, helping in the molecular characterization of oxidized species.

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Section: Resultsmentioning

confidence: 95%

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

et al. 2009

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“…Nevertheless, after the dihydrogen bonds were discovered, 176 intermolecular chemistry has expanded to new horizons, such as studies of solid state, catalysis, crystal engineering, and materials chemistry. [315][316][317] Among these, many other works about dihydrogen bonds 180,318,319 are conducted by means of theoretical analysis in small systems, [320][321][322] generally those where M is beryllium, aluminium, gallium, silicon, or germanium. 323a However, the literature reports that beryllium hydride (BeH 2 ) is the most efficient proton acceptor to be used in the formation of dihydrogen-bonded systems.…”

Section: Boaz Galdino De Oliveiramentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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In this paper, the intermolecular structural study asserted by the vibrational analysis in the stretch frequencies of hydrogen bonds (π···H) and dihydrogen bonds (H(-δ)···H(+δ)) have definitively been revisited by means of calculations carried out by Density Functional Theory (DFT) and topological parameters derived from the classic treatise of the Quantum Theory of Atoms in Molecules (QTAIM). As a matter of fact the π···H hydrogen bond is formed between the hydrofluoric acid and the C≡C bond of the acetylene, but the QTAIM calculations revealed a distortion in this interaction due to the formation of the ternary complex C(2)H(2)···2(HF). Although the π bonds of ethylene (C(2)H(4)), propylene (C(2)H(3)(CH(3))), and t-butylene (C(2)H(2)(CH(3))(2)) are considered proton acceptors, two hydrogen-bond types--π···H and C···H--can be observed. Over and above the analysis of the π hydrogen bonds, theoretical arguments also were used to discuss the red-shifts in the stretch frequencies of the binary dihydrogen complexes formed by BeH(2)···HX with X = F, Cl, CN, and CCH. Although a vibrational blue-shift in the stretch frequency of the H-C bond of HCF(3) due to the formation of the BeH(2)···HCF(3) dihydrogen complex was obtained, unmistakable red-shifts were detected in LiH···HCF(3), MgH(2)···HCF(3), and NaH···HCF(3). Moreover, the alkali-halogen bonds were identified in relation to the formation of the trimolecular systems NaH···2(HCF(3)) and NaH···2(HCCl(3)). At last, theoretical calculations and QTAIM molecular integrations were used to study a novel class of dihydrogen-bonded complexes (mC(2)H(5)(+)···nMgH(2) with m = 1 or 2 and n = 1 or 2) based in the insight that MgH(2) can bind with the non-localized hydrogen H(+δ) of the ethyl cation (C(2)H(5)(+)). In an overview, QTAIM calculations were applied to evaluate the molecular topography, charge density, as well as to interpret the shifted frequencies either to red or blue caused by the formation of the hydrogen bonds and dihydrogen bonds.

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“…It should be noted that the use of multicenter indices to characterize dihydrogen bonds was very recently studied by Giambiagi and Bultinck . It was found there that there is a very good correlation between the size of the multicenter indices on the one hand and the interaction energies on the other.…”

Section: Introductionmentioning

confidence: 99%

Interplay Between Hydrogen Bond Formation and Multicenter π-Electron Delocalization: Intermolecular Hydrogen Bonds

et al. 2008

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The interplay between aromatic electron delocalization and intermolecular hydrogen bonding is thoroughly investigated using multicenter delocalization analysis. The effect on the hydrogen bond strength of aromatic electron delocalization within the acceptor and donor molecules is determined by means of the interaction energies between monomers, calculated at the B3LYP/6-311++G(d,p) level of theory. This magnitude is compared to variations of multicenter electron delocalization indices and covalent hydrogen bond indices, which are shown to correlate perfectly with the relative values of the interaction energies for the different complexes studied. The multicenter electron delocalization indices and covalent bond indices have been computed using the quantum theory of atoms in molecules approach. All the hydrogen bonds are formed with oxygen as the acceptor atom; however, the atom bonded to the donor hydrogen has been either oxygen or nitrogen. The water-water complex is taken as reference, where the donor and acceptor molecular environments are modified by substituting the hydrogens and the hydroxyl group by phenol, furan, and pyrrole aromatic rings. The results here shown match perfectly with the qualitative expectations derived from the resonance model.

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Bond indices in dihydrogen bonds

Cited by 4 publications

References 43 publications

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Interplay Between Hydrogen Bond Formation and Multicenter π-Electron Delocalization: Intermolecular Hydrogen Bonds

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Bond indices in dihydrogen bonds

Cited by 4 publications

References 43 publications

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

New Insights on Chemical Oxidation of Single-Wall Carbon Nanotubes: A Theoretical Study

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

Interplay Between Hydrogen Bond Formation and Multicenter π-Electron Delocalization: Intermolecular Hydrogen Bonds

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Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds