Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

Astakhov, Andrey A.; Tsirelson, Vladimir G.

doi:10.1002/qua.25600

Cited by 7 publications

(13 citation statements)

References 138 publications

(232 reference statements)

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“…The non‐local density‐based descriptors 30–36 carry information about the mutual influence of electrons in spatially remote regions and detect subtle effects in chemical bonding. The source function (SF) 30,31 reveals the role of atoms, defined in terms of QTAIM, 37 in formation of H‐bonds 30 .…”

Section: Introductionmentioning

confidence: 99%

The explicit role of electron exchange in the hydrogen bonded molecular complexes

2021

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We applied a set of advanced bonding descriptors to establish the hidden electron density features and binding energy characteristics of intermolecular D HÁÁÁA hydrogen bonds (O HÁÁÁO, N HÁÁÁO and S HÁÁÁO) in 150 isolated and solvated molecular complexes. The exchange-correlation and Pauli potentials as well as corresponding local one-electron forces allowed us to explicitly ascertain how electron exchange defines the bonding picture in the proximity of the H-bond critical point. The electron density features of D HÁÁÁA interaction are governed by alterations in the electron localization in the H-bond region displaying itself in the exchange hole. At that, they do not depend on the variations in the exchange hole mobility. The electrostatic interaction mainly defines the energy of H-bonds of different types, whereas the strengthening/weakening of H-bonds in complexes with varying substituents depends on the barrier height of the exchange potential near the bond critical point. Energy variations between H-bonds in isolated and solvated systems are also caused the electron exchange peculiarities as follows from the corresponding potential and the interacting quantum atom analyses complemented by electron delocalization index calculations. Our approach is based on the bonding descriptors associated with the characteristics of the observable electron density and can be recommended for in-depth studies of non-covalent bonding. K E Y W O R D S electron density, hydrogen bond, IQA, potential acting on an electron in a molecule, QM/MM, QTAIM, source function 1 | INTRODUCTION Intermolecular hydrogen bonds (H-bonds) are of paramount importance in supramolecular chemistry, 1,2 crystal engineering 3 and biochemistry. 4 These noncovalent interactions have been intensively studied by various theoretical and experimental techniques 5-8 : ab initio calculations, 9,10 molecular dynamic modeling, 11 quantum mechanics/molecular mechanics calculations, 12 NMR and IR spectroscopy, 13-15 X-Ray and neutron diffraction 16-18 and thermochemical experiments. 19 Among theoretical approaches, the electron density 7,20-23 and energy decomposition analyses 7,24 are gaining considerable popularity in the studies of H-bonds in the isolated state, 25,26 solution 27 and solid state. 28,29 Lest us consider some of them shortly. The non-local density-based descriptors 30-36 carry information about the mutual influence of electrons in spatially remote regions and detect subtle effects in chemical bonding. The source function (SF) 30,31 reveals the role of atoms, defined in terms of QTAIM, 37 in formation of H-bonds. 30 It is successfully used for classification of the H-bonds and other noncovalent interactions 38,39 as well as for identification of molecular parts having the greatest impact on the electron density along the H-bonds. 40 The electron delocalization indices (DI) characterize the extent of electron-pair sharing between atoms 41 and measure the H-bond covalency. 7,42-45

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Section: Introductionmentioning

confidence: 99%

The explicit role of electron exchange in the hydrogen bonded molecular complexes

2021

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“…All three z ‐axis quantities in Figure b–d are so‐called response properties: they do not relate to conventional bond characteristics (such as the localization and delocalization of electrons), but rather to the unconventional way in which the bonds respond to external stimuli. In this light, it is interesting to mention recent studies on the electron organization of many‐electron systems in the context of linear response theory . They highlight the profound connection between variances in local electronic position and the momentum operators and the optical conductivity tensor—that is, between electron (de)localization in real and momentum space on the one hand, and the experimentally observable spectroscopic and conductivity properties on the other hand.…”

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confidence: 99%

A Quantum‐Mechanical Map for Bonding and Properties in Solids

et al. 2018

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solids; a "semiconductor" has a narrow bandgap across which electrons can be excited by light; these classifications are therefore based on measurable, macroscopic properties. A fingerprint of five coexisting identifiers was recently used to define a concept termed "metavalent" bonding (MVB): [4,5] metavalent solids show i) moderate electronic conductivity (≈10 2 -10 4 S cm −1 ); ii) increased coordination numbers incompatible with the (8-N) rule for semiconductors; iii) large optical dielectric constants, ε ∞ ; iv) large bond polarizability, as measured by Born effective charges, Z*; and v) large lattice anharmonicity, as measured by the Grüneisen parameter, |γ TO |. In terms of conductivity and coordination numbers, metavalent solids are therefore located between the covalent and metallic regimes-but they are distinctly different from both because they show anomalously large response properties [5] and a unique bond-breaking mechanism [4] not observed in either covalent or metallic solids. This definition based on a set of observable properties directly led to a revision of the "resonant bonding" model (which had previously been widely used to describe the bonding in PCMs [6] ) by showing that the response properties of PCMs are fundamentally different from those of resonantly bonded benzene and graphite. [5] A 2D map is created for solid-state materials based on a quantum-mechanical description of electron sharing and electron transfer. This map intuitively identifies the fundamental nature of ionic, metallic, and covalent bonding in a range of elements and binary compounds; furthermore, it highlights a distinct region for a mechanism recently termed "metavalent" bonding. Then, it is shown how this materials map can be extended in the third dimension by including physical properties of application interest. Finally, it is shown how the map coordinates yield new insight into the nature of the Peierls distortion in phase-change materials and thermoelectrics. These findings and conceptual approaches provide a novel avenue to tailor material properties. Materials DesignThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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“…Second, we explicitly reveal the electronic features in the active sites of the complexes. We apply the QTAIM 5,61 and other advanced bonding descriptors: source function, 11,62 Fermi hole, 15,63 electron delocalization indices, 16 delocalization tensor, 64 condensed linear response kernel 23 to analyze the QM part of each system, i.e. its active site.…”

Section: Methodsmentioning

confidence: 99%

“…Nevertheless, due to the semi-local nature of the ellipticity index, its proles fail to manifest effects of extensive electron delocalization in chemical bond picture. Therefore, to study electron delocalization in the N-C 4 -C 3 fragment in more detail and to reveal the inuence of the conjugated bonds in R 2 on the C 4 -C 3 bond in the NCF complexes, we applied the electron delocalization tensor D (see the ESI, † eqn (7)-(9)), 64 which is a quantitative measure of uncertainty in electrons' positions and reects various physical effects: from quantum uncertainty in position of each particle to mutual correlations in electron motion. The major eigenvalue of delocalization tensor density D(r), l 1 (r), expresses delocalization magnitude along the direction of maximum electron delocalization in a system.…”

Section: Analysis Of the C 3 ]C 4 Double Bond Formationmentioning

confidence: 99%

Revealing electronic features governing hydrolysis of cephalosporins in the active site of the L1 metallo-β-lactamase

et al. 2020

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Spatially resolved characterization of electron localization and delocalization in molecules: Extending the Kohn‐Resta approach

Cited by 7 publications

References 138 publications

The explicit role of electron exchange in the hydrogen bonded molecular complexes

The explicit role of electron exchange in the hydrogen bonded molecular complexes

A Quantum‐Mechanical Map for Bonding and Properties in Solids

Revealing electronic features governing hydrolysis of cephalosporins in the active site of the L1 metallo-β-lactamase

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