Structural and bond evolutions during a chemical reaction

Carpio‐Martínez, Pablo; Cortés‐Guzmán, Fernando

doi:10.1016/b978-0-323-90891-7.00016-5

Cited by 1 publication

(2 citation statements)

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“…Therefore, the charge of an atom in a molecule q is defined as the difference between the population of a free atom of the same element and the population of a bonded atom considered. The QTAIM turned out to be seminal and formed the basis of quantum chemical topology, , quantum crystallography, , and modern charge density studies − and chemistry. , …”

Section: Introductionmentioning

confidence: 99%

“…The QTAIM turned out to be seminal and formed the basis of quantum chemical topology, 9,10 quantum crystallography, 11,12 and modern charge density studies 13−17 and chemistry. 8,18 However, there is no unique quantum-mechanical definition of a chemical bond; 19,20 therefore, there are still discussions about the concept of chemical structures. Obviously, the formation and existence of every stable many-electron multinuclear system are provided by a fine balance of internuclear and electronic forces.…”

Section: ■ Introductionmentioning

confidence: 99%

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Unified Picture of Interatomic Interactions, Structures, and Chemical Reactions by Means of Electrostatic and Kinetic Force Density Fields: Appel’s Salt and Its Ion Pairs

Saifina

Kartashov

Stash

et al. 2023

Crystal Growth & Design

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This paper presents a binding approach based on the electrostatic and kinetic force density fields and proposed to elucidate interatomic interactions, structures, and chemical reactions. Among other elements, it consists in the understanding of (i) the arrangement of pseudoatomic zero-flux surfaces (ZFSs), (ii) the mutual compression of force-field pseudoatoms of the same type, (iii) the penetration of a bonded atom into neighboring forcefield pseudoatoms, (iv) the distortion of the force fields, and (v) the occurrence of a binding path connecting two force-field attractors as the inherent consequences of the emergence and existence of any many-electron multinuclear system. Herein, the interatomic charge transfer and the reciprocal quantum-chemical response accompanying the covalent and noncovalent bond formation were studied using the abovementioned penetration, exemplified by Appel's salt. Such consideration gave rise to the concept of force-induced "push−pull" assembling of interacting (pseudo)atoms. In this regard, various halogen, chalcogen, and tetrel noncovalent interactions, as well as polar covalent bonds, were examined. Furthermore, the notion of the force-based binding structure was proposed instead of the bonding one, which defines the mutual connectivity of force-field pseudoatoms of the same type via binding paths. The thus-defined chemical structure proved to be more sensitive to variations in the configuration space of nuclear coordinates. It was found that the three-center chalcogen bonding Cl − •••S−S and tetrel bonding Cl − •••C•••Cl − in the crystal studied resemble the initial and transition states of bimolecular nucleophilic substitution reactions, respectively. Their central atoms act as electron contributors with a different degree of the transferred electron density sharing. Being extracted from the crystal structure, the corresponding ion pairs undergo chemical rearrangement: Forming the covalent bonds Cl−S and Cl−C leads to the collapse of the pseudoatomic ZFSs and the alignment of the bond and binding paths in the internuclear regions.

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