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2016 | Book

Lewis and Kossel’s Legacy: Structure and Bonding in Main-Group Compounds Read chapter Read first chapter

The Chemical Bond II

100 Years Old and Getting Stronger

Editor: D. Michael P. Mingos

Publisher: Springer International Publishing

Book Series : Structure and Bonding

Part of: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik" , Springer Professional "Wirtschaft"

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About this book

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.
The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors

Table of Contents

Frontmatter
Lewis and Kossel’s Legacy: Structure and Bonding in Main-Group Compounds
Abstract
In this article the authors provide a brief review of the main developments in our understanding of chemical bonding in representative compounds of the main group elements from Lewis’ and Kossel’s shell-setting articles in 1916 and until the present.
Arne Haaland, Mats Tilset
Quantum Chemical Topology
Abstract
In this frank and thought-provoking account, quantum chemical topology (QCT) is explained to the novice, leading up highlights of QCT’s most recent findings and views. The difference between a topological atom and a quantum atom is explained. After some philosophical insights and historical material, equations start appearing in the second half, in order to explain topological energy partitioning. Special attention was paid to the clarity and completeness of these equations. This QCT approach is proposed as a minimal and reference-state-free method to interpret chemical bonding. The link between bond order and interatomic exchange energy is explicitly given and uses a multipole expansion. These two quantities are illustrated with quite a few numerical examples and the trends amongst them. Finally, the Laplacian of the electron density is briefly expounded, focusing on the so-called L-graph and how they heuristically support the Lewis pair model.
Paul L. A. Popelier
Electron Pairs in Position Space
Abstract
The electron pair is a central object in chemist's view of the chemical bond. The definition and description of the electron pair in the position space is a complex problem within the quantum chemistry. Several different possibilities of how to accomplish this task, i.e., how to describe the localizability of an electron and electron pair, are given in a historical survey. The derivation of the electron localizability indicator (ELI) is presented and the application of ELI for the bonding analysis is examined for few systems. The importance of the ELI-q describing the singlet-coupled electron pairs and its connection to Lewis idea of bonding is highlighted.
M. Kohout
New Landscape of Electron-Pair Bonding: Covalent, Ionic, and Charge-Shift Bonds
Abstract
We discuss here the modern valence bond (VB) description of the electron-pair bond vis-à-vis the Lewis–Pauling model and show that along the two classical families of covalent and ionic bonds, there exists a family of charge-shift bonds (CSBs) in which the “resonance fluctuation” of the electron-pair density plays a dominant role. A bridge is created between the VB description of bonding and three other approaches to the problem: the electron localization function (ELF), atoms-in-molecules (AIM), and molecular orbital (MO)-based theories. In VB theory, CSB manifests by repulsive or weakly bonded covalent state and large covalent–ionic resonance energy, RE CS. In ELF, it shows up by a depleted basin population with fluctuations and in AIM by a positive Laplacian. CSB is derivable also from MO-based theory. As such, CSB is shown to be a fundamental mechanism that satisfies the equilibrium condition of bonding, namely, the virial ratio of the kinetic and potential energy contributions to the bond energy. The chapter defines the atomic propensity for CSB and outlines its territory: Atoms (fragments) that are prone to CSB are compact electronegative and/or lone-pair-rich species. As such, the territory of CSB transcends considerations of static charge distribution, and it involves (a) homopolar bonds of heteroatoms with zero static ionicity, (b) heteropolar σ- and π-bonds of the electronegative and/or electron-pair-rich elements among themselves and to other atoms (e.g., the higher metalloids, Si, Ge, Sn, etc.), and (c) electron-rich hypercoordinate molecules. Several experimental manifestations of charge-shift bonding are discussed.
Sason Shaik, David Danovich, Benoit Braida, Wei Wu, Philippe C. Hiberty
The Relevance of the ELF Topological Approach to the Lewis, Kossel, and Langmuir Bond Model
Abstract
The electron localization function (ELF) approach to chemical bonding is revisited as a tool to check the falsifiability of the Lewis hypotheses. It is shown that the boundaries of the ELF basins correspond to zero-flux surfaces of the local integrated same spin pair probability enabling the determination of regions of the molecular space which maximizes the opposite spin pair density and therefore groups of electrons. The ELF yields a partition into core and valence basins which matches the Lewis model. The valence basins which correspond either to electron lone pairs or to bonds enable the definition of atomic valence shells in which bonding basins are shared by at least two atomic valence shells. The ELF basin populations take into account the mesomery which explains the deviations from ideal values. The organization of the basins around the atomic cores often complies with the VSEPR rules. The behavior of the ELF basins upon deformation of the nuclear frame sheds light onto the reactivity and reaction mechanisms, whereas the basin compressibilities provide chemical explanations of pressure-induced phase transitions.
Bernard Silvi
Comparison of the Cr–Cr Quadruple and Quintuple Bonding Mechanisms
Abstract
A molecular orbital analysis of model unbridged complexes with Cr–Cr formal bond orders four and five is presented, based on density functional calculations. The orbital and symmetry analysis discloses a special type of δ bonding in the case of the [Cr2L4]2+ complexes that induces a significant bond shortening going from quadruple CrII–CrII to quintuple CrI–CrI bonds.
Andrés Falceto, Santiago Alvarez
Backmatter
Metadata
Title
The Chemical Bond II
Editor
D. Michael P. Mingos
Copyright Year
2016
Electronic ISBN
978-3-319-33522-3
Print ISBN
978-3-319-33520-9
DOI
https://doi.org/10.1007/978-3-319-33522-3

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