On the Nature of the Bonding in Coinage Metal Halides

This article analyzes the nature of the chemical bond in coinage metal halides using high-level ab initio Valence Bond (VB) theory. It is shown that these bonds display a large Charge-Shift Bonding character, which is traced back to the large Pauli pressure arising from the interaction between the bond pair with the filled semicore d shell of the metal. The gold-halide bonds turn out to be pure Charge-Shift Bonds (CSBs), while the copper halides are polar-covalent bonds and silver halides borderline cases. Among the different halogens, the largest CSB character is found for fluorine, which experiences the largest Pauli pressure from its σ lone pair. Additionally, all these bonds display a secondary but non-negligible π bonding character, which is also quantified in the VB calculations.

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Identifying Ionic and Polar Covalent Bonds in Superionic Metal Halides

ECS Meeting Abstracts ◽

10.1149/ma2021-016410mtgabs ◽

2021 ◽

Vol MA2021-01 (6) ◽

pp. 410-410

Author(s):

Oskar Kenyatta Garcia ◽

Johana Dolores Aleman ◽

Nicole Adelstein

Keyword(s):

Metal Halides ◽

Covalent Bonds

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ChemInform Abstract: THE ELECTRONIC STRUCTURE OF PYRAZINE, A VALENCE BOND MODEL FOR LONE PAIR INTERACTIONS

Chemischer Informationsdienst ◽

10.1002/chin.197526089 ◽

1975 ◽

Vol 6 (26) ◽

Author(s):

WILLARD R. WADT ◽

WILLIAM A. III GODDARD

Keyword(s):

Electronic Structure ◽

Valence Bond ◽

Lone Pair ◽

Bond Model ◽

Lone Pair Interactions ◽

Pair Interactions

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Die Eignung einiger Übergangsmetallhalogenide als Kathodenmaterialien / The Suitability of Some Transition Metal Halides as Cathode Materials

Zeitschrift für Naturforschung B ◽

10.1515/znb-1973-11-1213 ◽

1973 ◽

Vol 28 (11-12) ◽

pp. 763-771 ◽

Cited By ~ 5

Author(s):

Günter Eichinger ◽

Heinz P. Fritz

Keyword(s):

Cyclic Voltammetry ◽

Transition Metal ◽

Cathode Materials ◽

High Energy ◽

Metal Halides ◽

Silver Halides ◽

Chloro Complexes ◽

Potentiometric Titrations ◽

Halide Complexes ◽

Copper Halides

Some transition metal halides are tested for their suitability as cathode materials in secondary high energy batteries. The solubilities of the silver halides are determined colorimetrically. Furthermore the generation of halide complexes of silver and copper halides in different electrolytes is tested by cyclic voltammetry. It is shown, that with silver and copper halides in different electrolytes, even in a solution of 1 ᴍ LiAlCl4 in PC halide complexes are formed, which rapidly diffuse from the working electrode. The generated chloro complexes were determined by potentiometric titrations as AgCl2, CuCl2 and CuCl2-4. The use of other transition metal halides is also considered.

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The hydrogen abstraction reaction H + C2H6 → H2(v,j) + C2H5. Part I. A full-dimensional analytical potential energy surface based on ab initio calculations

Physical Chemistry Chemical Physics ◽

10.1039/c9cp00699k ◽

2019 ◽

Vol 21 (24) ◽

pp. 13347-13355 ◽

Cited By ~ 3

Author(s):

Joaquin Espinosa-Garcia ◽

Moises Garcia-Chamorro ◽

Jose C. Corchado

Keyword(s):

Potential Energy ◽

Potential Energy Surface ◽

Energy Surface ◽

Hydrogen Abstraction ◽

Level Structure ◽

Valence Bond ◽

Abstraction Reaction ◽

Analytical Potential ◽

High Level ◽

Hydrogen Abstraction Reaction

Using as input data high-level structure electronic calculations, a new full-dimensional analytical potential energy surface (PES), named PES-2018, was developed for the title reaction, which is a valence bond/molecular mechanics based surface that depends on a set of adjustable parameters.

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d Orbitals in the noble-gas dihalides

Canadian Journal of Chemistry ◽

10.1139/v70-455 ◽

1970 ◽

Vol 48 (17) ◽

pp. 2695-2701 ◽

Cited By ~ 8

Author(s):

R. C. Catton ◽

K. A. R. Mitchell

Keyword(s):

Noble Gas ◽

Valence Bond ◽

Ionic Character ◽

Orbital Exponent ◽

Covalent Bonds ◽

Model Calculations ◽

Pair Bonds ◽

Electron Repulsion Integrals ◽

D Orbitals

Model calculations are reported for ArF2, KrF2, XeF2, ArCl2, KrCl2, and XeCl2. The approach is to compare the energies of a number of valence-bond structures for each molecule. The calculations use Slater-type radial functions and simplify the electron repulsion integrals with the Mulliken approximation. Energies are optimized by varying the d orbital exponent and a parameter which governs the ionic character of the covalent bonds. For all the molecules it is found that the structures such as (X—M+X− + X−M+—X) and X−M2+X−, which maintain the octet rule and exclude the use of d orbitals, are less stable than the structure X—M—X which implies localized electron-pair bonds based on pd hybrids at the noble-gas atom M.Approximate molecular wave functions are obtained from a configuration interaction calculation, and the general conclusion is that the valence-bond structures incorporating d orbitals become more important as the atomic number of the central atom increases. A preliminary study of the role of the [Formula: see text] orbital is also presented, but it seems this orbital contributes mainly as a polarization effect.

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On the nature of M–CO(lone pair)⋯π(arene) interactions in the solid state of fluorinated oxaphosphirane complexes

CrystEngComm ◽

10.1039/c5ce01331c ◽

2015 ◽

Vol 17 (35) ◽

pp. 6736-6743 ◽

Cited By ~ 8

Author(s):

Cristina Murcia-García ◽

Antonio Bauzá ◽

Antonio Frontera ◽

Rainer Streubel

Keyword(s):

Solid State ◽

Dft Calculations ◽

Lone Pair ◽

X Ray ◽

High Level

The X-ray structures of several oxaphosphirane tungsten(0) complexes exhibit interesting intramolecular W–CO(lone pair)ċπ(arene) interactions that have been rationalized by means of high-level DFT calculations and the CSD.

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A theoretical-electron-density databank using a model of real and virtual spherical atoms

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520617008204 ◽

2017 ◽

Vol 73 (4) ◽

pp. 610-625 ◽

Cited By ~ 3

Author(s):

Ayoub Nassour ◽

Slawomir Domagala ◽

Benoit Guillot ◽

Theo Leduc ◽

Claude Lecomte ◽

...

Keyword(s):

Charge Density ◽

Electron Density ◽

Density Functional ◽

Lone Pair ◽

Density Functional Theory Calculations ◽

Ligand Complex ◽

Urea Molecule ◽

Covalent Bonds ◽

Similar Chemical ◽

Chemical Groups

A database describing the electron density of common chemical groups using combinations of real and virtual spherical atoms is proposed, as an alternative to the multipolar atom modelling of the molecular charge density. Theoretical structure factors were computed from periodic density functional theory calculations on 38 crystal structures of small molecules and the charge density was subsequently refined using a density model based on real spherical atoms and additional dummy charges on the covalent bonds and on electron lone-pair sites. The electron-density parameters of real and dummy atoms present in a similar chemical environment were averaged on all the molecules studied to build a database of transferable spherical atoms. Compared with the now-popular databases of transferable multipolar parameters, the spherical charge modelling needs fewer parameters to describe the molecular electron density and can be more easily incorporated in molecular modelling software for the computation of electrostatic properties. The construction method of the database is described. In order to analyse to what extent this modelling method can be used to derive meaningful molecular properties, it has been applied to the urea molecule and to biotin/streptavidin, a protein/ligand complex.

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