Electron-pairing analysis from localization and delocalization indices in the framework of the atoms-in-molecules theory

Fradera, Xavier; Poater, Jordi; Simon, Sı́lvia; Duran, Miquel; Solà, Miquel

doi:10.1007/s00214-002-0375-5

Cited by 179 publications

(123 citation statements)

References 3 publications

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“…Currently, the best available indices to probe the nature of bonding between the AIM are the electronic delocalization index (e-DI), [75][76][77][78][79][80] and the energy partitioning based on the Interacting Quantum Atoms (IQA) methodology. [81][82][83][84][85] The extended version of the delocalization indices and certain elements of the extended IQA, introduced within the context of the MC-QTAIM, have been reported elsewhere.…”

Section: Resultsmentioning

confidence: 99%

On the Nature of the Positronic Bond

Goli

Shahbazian

2019

ChemPhysChem

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Recently it has been proposed that the positron, the anti‐particle analog of the electron, is capable of forming an anti‐matter bond in a composite system consists of two hydride anions and a positron [Angew. Chem. Int. Ed. 57, 8859–8864 (2018)]. In order to dig into the nature of this novel bond the newly developed multi‐component quantum theory of atoms in molecules (MC‐QTAIM) is applied to this positronic system. The topological analysis reveals that this species is composed of two atoms in molecules, each containing a proton and half of the electronic and the positronic populations. Further analysis elucidates that the electron exchange phenomenon is virtually non‐existent between the two atoms and no electronic covalent bond is conceivable in between. On the other hand, it is demonstrated that the positron density enclosed in each atom is capable of stabilizing interactions with the electron density of the neighboring atom. This electrostatic interaction suffices to make the whole system bonded against all dissociation channels. Thus, the positron indeed acts like an anti‐matter glue between the two atoms.

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Section: Resultsmentioning

confidence: 99%

On the Nature of the Positronic Bond

Goli

Shahbazian

2019

ChemPhysChem

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“…However, the extent of the electron sharing between the ions and the π-systems can be quantified via delocalization index, DI, 54,55,56,57,58,59 as is defined within the context of the theory of atoms in molecules, Figure S2. The DI increases by increasing the field strength as it has been observed in our previous studies, 26,27 suggesting an enhancement of the electron sharing between the ions and the π-system.…”

Section: Charge-transfer Excited-states and Bond Strengthening In Thementioning

confidence: 99%

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Novák

Foroutan‐Nejad

Marek

2016

J. Chem. Theory Comput.

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Substituted coronenes, a family of ion-π receptors whose ion-affinities can be explained exclusively neither via ion-quadrupole nor induction/polarization mechanisms, are studied. The best descriptors of ion-affinity among these species are those characterizing charge-transfer between ions and the π-systems, e.g. vertical ionization potential, electron affinity, and the relative energies of charge-transfer excited-states (CTESs). The variation of the electric multipole moments, polarizability, binding energy, and relative energy of CTESs in the presence of an external electric field (EEF) is evaluated. The results indicate that the EEF has a negligible effect on the polarizability and quadrupole moment of the systems. However, it significantly affects the binding energies, CTES energies, and the dipole moments of the receptors. Contrary to the changes in the dipole moment, the variation pattern of the binding energy is more consistent with the pattern observed for the CTES energy changes. Finally, by analyzing the exchange-correlation component of the binding energy we demonstrate that the increased binding energy, i.e. bond strengthening, originates from enhanced electron sharing and multicenter covalency between the ions and the π-systems as a result of the state-mixing between the ground-state and the CTESs. According to our findings, we hypothesize that the electron sharing and in extreme cases the multicenter covalency are the main driving forces for complexation of ions with extended π-receptors such as carbon nanostructures.

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“…The e value of 4a (0.232) is close to the value of the 1.5-fold bond. The delocalisation index (DI), [27,28] which may be regarded as ac ovalent bond order,i sc lose to the value of ap ure single bond (1.0) in 3a and increases from 4a to 5.Inthe context of the QTAIM analysis,i ti si nteresting that the two intramolecular N À H···O hydrogen bonds in compound 4a (Figure 3A)a re strong and include covalent contributions, indicated by significant electron-density accumulations at the H···O bond-critical points (1 BCP = 0.258 and 0.263 e À3 with 5 2 1 BCP = 2.78 and 2.53 e À5 ,r espectively). These are signs of resonance-assisted hydrogen bonds which close asixmembered ring here and facilitate electron delocalisation in the system.…”

Section: Angewandte Chemiementioning

confidence: 99%

Chemical Bonding in Polarised Push–Pull Ethylenes

et al. 2019

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1,1-Diamino-2,2-bis(triflyl)ethylenes with both twisted and planar structures around the partial "C = C" bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high-resolution X-ray diffraction data treated with X-ray wavefunction refinement (XWR). In the twisted compound, adominant contribution of the charge-separated resonance structure was revealed. On the contrary,t he nearly planar compound still showed pbonding character,h owever,w ith ac onsiderable contribution of the charge-separated resonance structure.

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Electron-pairing analysis from localization and delocalization indices in the framework of the atoms-in-molecules theory

Cited by 179 publications

References 3 publications

On the Nature of the Positronic Bond

On the Nature of the Positronic Bond

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Chemical Bonding in Polarised Push–Pull Ethylenes

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