A comparative view on the potential acting on an electron in a molecule and the electrostatic potential through the typical halogen bonds

Барташевич, Е. В.; Tsirelson, Vladimir G.

doi:10.1002/jcc.25112

Cited by 40 publications

(41 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…We have recently proposed the potential acting on an electron in molecule (PAEM [36]) [37] as a function that not only characterizes the properties of non-covalent bonding with a significant electrostatic component, but also allows us to observe the quantitative relationship with the interaction energy in complexes. Unlike ESP, the PAEM contains both Coulomb and exchange components.…”

Section: Introductionmentioning

confidence: 99%

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

2019

Self Cite

View full text Add to dashboard Cite

The consideration of the disposition of minima of electron density and electrostatic potential along the line between non-covalently bound atoms in systems with Hal−···CH3–Y (Hal− = Cl, Br; Y = N, O) fragments allowed to prove that the carbon atom in methyl group serves as an electrophilic site provider. These interactions between halide anion and carbon in methyl group can be categorized as the typical tetrel bonds. Statistics of geometrical parameters for such tetrel bonds in CSD is analyzed. It is established that the binding energy in molecular complexes with tetrel bonds correlate with the potential acting on an electron in molecule (PAEM). The PAEM barriers for tetrel bonds show a similar behavior for both sets of complexes with Br− and Cl− electron donors.

show abstract

Section: Introductionmentioning

confidence: 99%

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…[72][73][74] In this manuscript, we report results for the homonuclear diatomic molecules from Period 2 using all these methods. Moreover, we have calculated potential acting on one electron molecular orbitals (PAEM-MO) [75][76][77][78] and the electrostatic potential (ESP) for the diatomic molecules. Interestingly, these methods provide a universal way to look at the bonds holding the Period 2 atoms together when they form a diatomic molecule.…”

Section: Introductionmentioning

confidence: 99%

Chemical bonding in Period 2 homonuclear diatomic molecules: a comprehensive relook

Das

Arunan

2019

J Chem Sci

View full text Add to dashboard Cite

Theoretical and experimental studies of bonding in the main group homonuclear diatomic molecules have been pursued for many years, and they possess serious challenges for scientists. Most of the early experimental work have been carried out by Herzberg. 1,2 We take a relook at the bonding motifs of Period 2 homonuclear diatomic molecules (from Li 2 to Ne 2) using varieties of quantum chemical tools, commonly used for intermolecular bonding/interactions now. The methods employed include Atoms in Molecules (AIM), Non-covalent Index plot (NCI), Electrostatic potential (ESP), and Potential Acting on one Electron in a Molecule (PAEM). The spectroscopic constants i.e., equilibrium bond distances (r e), harmonic frequencies (x), bond dissociation energies (D e) have all been evaluated using high-level ab initio methods and critically compared with the experimental results. Multi-reference calculations (CASSCF) on B 2 and C 2 have been carried out as they have a large number of low lying electronic states. Bonding within these homonuclear diatomic molecules show all the diversities that are encountered in inter/intra-molecular bonding in chemistry. Based on the AIM analysis, these 8 homonuclear diatomic molecules could be divided into three different groups, based on the correlation between binding energy and the electron density at the bond critical point. However, PAEM/ESP analysis allows us to analyse all eight of them as one group having a good correlation between binding energy and the PAEM/ESP at the critical point between the two atoms. Our results highlight the arbitrariness in relying on some computational tools to characterize a bond as covalent (shared) or ionic/electrostatic (closed). In contrast, they also show the usefulness of the various methods in exploring similarities and differences in bonding. We propose that from Li 2 to Ne 2 , all homonuclear diatomic molecules are bound by 'chemical bonds'.

show abstract

“…The potential v s (r) = v PAEM (r) acts on an electron belonging to a molecule (PAEM) (Yang & Davidson, 1997;Zhao & Yang, 1999;Zhang et al, 2005;Gong & Yang, 2010;Zhao & Yang, 2014a;Zhao, Yan et al, 2018). Zhao et al 2002Zhao et al , 2005Zhao & Yang, 2008, 2014bBartashevich & Tsirelson, 2018). It is the average local potential energy of any one (indistinguishable) internal electron located at point r; with the remaining electrons and all nuclei of a system (Zhao & Yang, 2014;Martin Pendas et al, 2016):…”

Section: Methodsmentioning

confidence: 99%

Orbital-free quantum crystallography: view on forces in crystals

Tsirelson

Stash

2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

Self Cite

View full text Add to dashboard Cite

Quantum theory of atoms in molecules and the orbital-free density functional theory (DFT) are combined in this work to study the spatial distribution of electrostatic and quantum electronic forces acting in stable crystals. The electron distribution is determined by electrostatic electron mutual repulsion corrected for exchange and correlation, their attraction to nuclei and by electron kinetic energy. The latter defines the spread of permissible variations in the electron momentum resulting from the de Broglie relationship and uncertainty principle, as far as the limitations of Pauli principle and the presence of atomic nuclei and other electrons allow. All forces are expressed via kinetic and DFT potentials and then defined in terms of the experimental electron density and its derivatives; hence, this approach may be considered as orbital-free quantum crystallography. The net force acting on an electron in a crystal at equilibrium is zero everywhere, presenting a balance of the kinetic F kin( r ) and potential forces F ( r ). The critical points of both potentials are analyzed and they are recognized as the points at which forces F kin( r ) and F ( r ) individually are zero (the Lagrange points). The positions of these points in a crystal are described according to Wyckoff notations, while their types depend on the considered scalar field. It was found that F ( r ) force pushes electrons to the atomic nuclei, while the kinetic force F kin( r ) draws electrons from nuclei. This favors formation of electron concentration bridges between some of the nearest atoms. However, in a crystal at equilibrium, only kinetic potential v kin( r ) and corresponding force exhibit the electronic shells and atomic-like zero-flux basins around the nuclear attractors. The force-field approach and quantum topological theory of atoms in molecules are compared and their distinctions are clarified.

show abstract

A comparative view on the potential acting on an electron in a molecule and the electrostatic potential through the typical halogen bonds

Cited by 40 publications

References 56 publications

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

Chemical bonding in Period 2 homonuclear diatomic molecules: a comprehensive relook

Orbital-free quantum crystallography: view on forces in crystals

Contact Info

Product

Resources

About