Orbital‐Free Quantum Crystallographic View on Noncovalent Bonding: Insights into Hydrogen Bonds, π⋅⋅⋅π and Reverse Electron Lone Pair⋅⋅⋅π Interactions

Shteingolts, Sergey A.; Сташ, А. И.; Tsirelson, Vladimir G.; Fayzullin, Robert R.

doi:10.1002/chem.202005497

Cited by 41 publications

(174 citation statements)

References 159 publications

(333 reference statements)

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“…2a). Also, the local negative maxima between the K and L shells and a bond midpoint plateau between atoms are observed in agreement with results of the others (Baerends & Gritsenko, 1997;Bartashevich & Tsirelson, 2018;Levina et al, 2021;Shteingolts et al, 2021). These local maxima become less evident when LDA is used for v x (r).…”

Section: Resultssupporting

confidence: 88%

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Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Tsirelson¹,

Сташ²

2021

Acta Crystallogr B Struct Sci Cryst Eng Mater

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This work extends the orbital-free density functional theory to the field of quantum crystallography. The total electronic energy is decomposed into electrostatic, exchange, Weizsacker and Pauli components on the basis of physically grounded arguments. Then, the one-electron Euler equation is re-written through corresponding potentials, which have clear physical and chemical meaning. Partial electron densities related with these potentials by the Poisson equation are also defined. All these functions were analyzed from viewpoint of their physical content and limits of applicability. Then, they were expressed in terms of experimental electron density and its derivatives using the orbital-free density functional theory approximations, and applied to the study of chemical bonding in a heteromolecular crystal of ammonium hydrooxalate oxalic acid dihydrate. It is demonstrated that this approach allows the electron density to be decomposed into physically meaningful components associated with electrostatics, exchange, and spin-independent wave properties of electrons or with their combinations in a crystal. Therefore, the bonding information about a crystal that was previously unavailable for X-ray diffraction analysis can be now obtained.

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Section: Resultssupporting

confidence: 88%

“…After many years of intensive research, the orbital-free DFT now finds an application in various scientific fields (Wesolowski & Wang, 2013;Mi et al, 2018;Shteingolts et al, 2021;Bartashevich et al, 2021). In this work, we aimed to analyze the properties inherent to each function of orbital-free DFT relevant to quantum crystallography.…”

Section: Discussionmentioning

confidence: 99%

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Tsirelson¹,

Сташ²

2021

Acta Crystallogr B Struct Sci Cryst Eng Mater

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“…To get more insight into the mechanisms of chemical bond formation beyond the orthodox topological analysis of electron density (ED) 𝜌(𝒓), we focus in this work on the analysis of electronic potentials 𝜑 𝑖 (𝒓) and corresponding local forces 𝑭 𝑖 (𝒓) 15,22,23 within the framework of quantum crystallography. [24][25][26][27][28][29][30][31] The orbital-free branch of quantum crystallography makes it possible to operate with ED and its derivatives, obtained either from theoretical calculations or experimental diffraction data for a many-electron multinuclear system in the stationary ground state.…”

Section: Introductionmentioning

confidence: 99%

“…22,55 In the ∇𝜑 𝑒𝑠 -and ∇𝜑 𝑘 -fields, there are 𝜑 𝑒𝑠 -or 𝜑 𝑘 -paths, each of which consists of a pair of gradient lines originating at a CP (3, -1) and terminating at two neighboring CPs (3, -3). 15 3D attractors of the electronic force fields, i.e., CPs (3, -3), coincide with positions of atomic nuclei, which allows one to attribute considered 𝜑-basins to specific atoms within a molecule or a crystal. At that, 𝜑 𝑒𝑠 -basins enclose all electric field lines starting at corresponding nuclei and define electrically neutral pseudoatoms.…”

mentioning

confidence: 99%

Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields

Shteingolts

Stash

Tsirelson

et al. 2022

Preprint

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Intricate behavior of one-electron potentials from the Euler equation for electron density and corresponding gradient force fields in crystals was studied. Bosonic and fermionic quantum potentials were utilized in bonding analysis as descriptors of the localization of electrons and electron pairs. Channels of locally enhanced kinetic potential and the corresponding saddle Lagrange points were found between chemically bonded atoms linked by the bond paths. Superposition of electrostatic φ_es (r) and kinetic φ_k (r) potentials and electron density ρ(r) allowed partitioning any molecules and crystals into atomic ρ- and potential-based φ-basins; the φ_k-basins explicitly account for electron exchange effect, which is missed for φ_es-ones. Phenomena of interatomic charge transfer and related electron exchange were explained in terms of space gaps between ρ- and φ-zero-flux surfaces. The gap between φ_es- and ρ-basins represents the charge transfer, while the gap between φ_k- and ρ-basins is proposed to be a real-space manifestation of sharing the transferred electrons. The position of φ_k-boundary between φ_es- and ρ-ones within an electron occupier atom determines the extent of electron sharing. The stronger an H‧‧‧O hydrogen bond is, the deeper hydrogen atom’s φ_k-basin penetrates oxygen atom’s ρ-basin. For covalent bonds, a φ_k-boundary closely approaches a φ_es-one indicating almost complete sharing the transferred electrons, while for ionic bonds, the same region corresponds to electron pairing within the ρ-basin of an electron occupier atom.

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“…The aim of this article is to make this issue clearer. We will present a detailed analysis of the distribution of electron density, chemical bonding and the anharmonicity of atomic displacements in the ferroelectric phase of KNO based on the results of a precise X-ray diffraction experiment on a perfect stoichiometric single crystal, and also a detailed study of the picture and nature of the distribution of the innercrystal field in this crystal based on the approach described by , Shteingolts et al (2021) and Bartashevich et al (2021). The experimental data are compared with the results of the theoretical calculation of KNO by the Kohn-Sham method with periodic boundary conditions.…”

Section: Introductionmentioning

confidence: 99%

X-ray diffraction study of the atomic interactions, anharmonic displacements and inner-crystal field in orthorhombic KNbO₃

Сташ¹,

Terekhova²,

Иванов³

et al. 2021

Acta Crystallogr B Struct Sci Cryst Eng Mater

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An X-ray diffraction study aimed at establishing the subtle details of the electron density and anharmonicity of the atomic vibrations in a stoichiometric monodomain single crystal of potassium niobate, KNbO3, has been conducted at room temperature (orthorhombic ferroelectric phase Amm2). The cation and anion displacements obtained from the experiment are weakly anharmonic without any manifestation of structural disorder. The chemical bond and interatomic interactions inside and between crystal substructures at the balance of intracrystalline forces are characterized in detail. The role of each of the ions in the formation of the ferroelectric phase was studied and the features of the electron-density deformation in the niobium and oxygen substructures, and the role of each of them in the occurrence of spontaneous polarization are established. The position-space distribution of electrostatic and quantum forces in KNbO3 is restored. It is emphasized that for the completeness of the analysis of the nature of the ferroelectric properties it is necessary to consider both static and kinetic electronic factors, which are of a quantum origin. The experimental results and theoretical estimations by the Kohn–Sham calculation with periodic boundary conditions are in reasonable agreement, thus indicating the physical significance of the findings of this study.

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Orbital‐Free Quantum Crystallographic View on Noncovalent Bonding: Insights into Hydrogen Bonds, π⋅⋅⋅π and Reverse Electron Lone Pair⋅⋅⋅π Interactions

Cited by 41 publications

References 159 publications

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields

X-ray diffraction study of the atomic interactions, anharmonic displacements and inner-crystal field in orthorhombic KNbO₃

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Orbital‐Free Quantum Crystallographic View on Noncovalent Bonding: Insights into Hydrogen Bonds, π⋅⋅⋅π and Reverse Electron Lone Pair⋅⋅⋅π Interactions

Cited by 41 publications

References 159 publications

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Developing orbital-free quantum crystallography: the local potentials and associated partial charge densities

Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields

X-ray diffraction study of the atomic interactions, anharmonic displacements and inner-crystal field in orthorhombic KNbO3

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X-ray diffraction study of the atomic interactions, anharmonic displacements and inner-crystal field in orthorhombic KNbO₃