Hydrogen Bonding—New Insights

Grabowski, Sławomir J.

doi:10.1007/978-1-4020-4853-1

Cited by 503 publications

(4 citation statements)

References 98 publications

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“…Atomic polarization and charge transfer as well as dispersion and exchange effect must be considered. Various aspects of the nature of hydrogen bonds are described in detail elsewhere. − Rephrasing the provisions of the previous paragraph, we can assert that the electron population within the space gap between neighboring ρ- and φ k -basins is a measure of covalency for any polar interaction. Armed with this yardstick, we are now in a position to get a reasonable answer to the question posed by the title of the review article, “What Is the Covalency of Hydrogen Bonding?”, by Grabowski …”

Section: Introductionmentioning

confidence: 94%

Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole

Kartashov

Shteingolts

Stash

et al. 2023

Crystal Growth & Design

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Herein, we experimentally obtained and studied the inner-crystal scalar potential fields and the associated vector force fields of static and kinetic nature in picolinic acid N-oxide (PANO) and methimazole. The “through-bond” and “through-space” electronic effects were defined and distinguished via the vector fields and concurred with the penetration of the electron contributor’s electrostatic and kinetic force field pseudoatoms (φes- and φ k -basins) into the occupier’s chemical atom (ρ-basin). A special focus was given to the dipolar N+–O– bond as well as to the thioamide N–CS and carboxylic OC–OH fragments. An unusual way of interatomic charge transfer was revealed between two nonbonded hydrogen atoms [COO−]H···H[−C] in the PANO crystal. The experimental electric and kinetic force fields in the molecular crystals were compared to the theoretical ones for the free molecules and hydrogen-bonded associates, which helped figure out the natural consequences of the crystal packing effect. As expected, the appearance of neighboring attractors in a dense crystal packing requires zero-flux surfaces (ZFSs) emerging in the vector fields and the compression of the outer force field pseudoatoms of a molecule. We proposed to consider a ZFS in the kinetic force field to be a turning surface for electrons in the sense that an electron passed through the boundary is immediately affected by the redirected force attributed to another attractor. The strengthening and noticeable increase observed in the covalency of the intramolecular hydrogen bond O–H···O in the PANO crystal is a direct consequence of such compression of the hydrogen atom and pseudoatoms by the inner-crystal environment. The Pauli and fermionic scalar and vector fields were applied to locate electron lone pairs and describe their involvement in noncovalent interactions within the donor–acceptor mechanism.

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Section: Introductionmentioning

confidence: 94%

Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole

Kartashov

Shteingolts

Stash

et al. 2023

Crystal Growth & Design

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“…With its clearly constructed formalism through which to identify an atom's boundary, QTAIM brings clarity and consistency to a number of previously ill defined chemical concepts such as the energies, sizes and electron counts of the atoms comprising a molecule or solid. However, the topological representation of chemical bonding ensuing from this theory is plagued by an ongoing debate-both questioning [6,[29][30][31][32] and supporting [33][34][35][36][37][38] its rigor and utility. It should be noted however, that the topological approach to bond analysis due to QTAIM neglects the central attribute of the theory-the partitioning of charge density into regions with well-characterized energies.…”

Section: Introductionmentioning

confidence: 99%

Observing the 3D Chemical Bond and its Energy Distribution in a Projected Space

et al. 2019

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Our curiosity‐driven desire to “see” chemical bonds dates back at least one‐hundred years, perhaps to antiquity. Sweeping improvements in the accuracy of measured and predicted electron charge densities, alongside our largely bondcentric understanding of molecules and materials, heighten this desire with means and significance. Here we present a method for analyzing chemical bonds and their energy distributions in a two‐dimensional projected space called the condensed charge density. Bond “silhouettes” in the condensed charge density can be reverse‐projected to reveal precise three‐dimensional bonding regions we call bond bundles. We show that delocalized metallic bonds and organic covalent bonds alike can be objectively analyzed, the formation of bonds observed, and that the crystallographic structure of simple metals can be rationalized in terms of bond bundle structure. Our method also reproduces the expected results of organic chemistry, enabling the recontextualization of existing bond models from a charge density perspective.

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“…), while previous reports gave positive value (about 0.002 a.u.). [31,65,66] Though in either case its magnitude is small and satisfies the H-bonding criterion of |H c |, [31,67] the sign-changing of implies the inconsistence in classifying the H-bonding into partiallycovalent and noncovalent interaction strictly according to criteria introduced above. This discrepancy might be mainly attributed to different sizes of basis sets in producing the electron density.…”

Section: Zpv Fluctuation Of Electronic-structure Featuresmentioning

confidence: 99%

Zero-point fluctuation of hydrogen bond in water dimer from ab initio molecular dynamics*

Jiang¹,

Wang²,

Ren³

et al. 2020

Chinese Phys. B

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Dynamic nature of hydrogen bond (H-bond) is central in molecular science of substance transportation, energy transfer, and phase transition in H-bonding networks diversely expressed as solution, crystal, and interfacial systems, thus attracting the state-of-the-art revealing of its phenomenological edges and sophisticated causes. However, the current understanding of the ground-state fluctuation from zero-point vibration (ZPV) lacks a firm quasi-classical base, concerning three basic dimensions as geometry, electronic structure, and interaction energy. Here, based on the ab initio molecular dynamics simulation of a ground-state water dimer, temporally separated fluctuation features in the elementary H-bond as the long-time weakening and the minor short-time strengthening are respectively assigned to two low-frequency intermolecular ZPV modes and two O–H stretching ones. Geometrically, the former modes instantaneously lengthen H-bond up to 0.2 Å whose time-averaged effect coverages to about 0.03 Å over 1-picosecond. Electronic-structure fluctuation crosses criteria’ borders, dividing into partially covalent and noncovalent H-bonding established for equilibrium models, with a 370% amplitude and the district trend in interaction energy fluctuation compared with conventional dragging models using frozen monomers. Extended physical picture within the normal-mode disclosure further approaches to the dynamic nature of H-bond and better supports the upper-building explorations towards ultrafast and mode-specific manipulation.

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Hydrogen Bonding—New Insights

Cited by 503 publications

References 98 publications

Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole

Electronic and Crystal Packing Effects in Terms of Static and Kinetic Force Field Features: Picolinic Acid N-Oxide and Methimazole

Observing the 3D Chemical Bond and its Energy Distribution in a Projected Space

Zero-point fluctuation of hydrogen bond in water dimer from ab initio molecular dynamics*

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