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Toward a physical understanding of electron-sharing two-center bonds. II. Pseudo-potential based analysis of diatomic molecules

TitleToward a physical understanding of electron-sharing two-center bonds. II. Pseudo-potential based analysis of diatomic molecules
Publication TypeJournal Article
Year of Publication2010
AuthorsBitter T, Wang SG, Ruedenberg K, Schwarz WHE
Journal TitleTheoretical Chemistry Accounts
Volume127
Pages237-257
Date Published10
ISBN Number1432-881X
Accession NumberISI:000282508000015
Keywordsbond energy analysis, bond types, charge distributions, CHEMICAL DEFORMATION DENSITIES, covalence, diatomics, effective core potentials, energy decomposition scheme, polar bond, pseudo-potentials, pseudopotential method, qu, transition-state method, x-ray
Abstract

A dozen homo- and heteropolar bonds in a series of diatomic molecules are analyzed by an energy partitioning based on the concepts developed in part I of this series (J Comput Chem 28:411-422, 2007). The different bond types are characterized by various physical contributions to the bond energy, namely classical potential interaction, quantum-mechanical orbital interference, and bond stabilizations by atomic configurational promotion, radial deformation, and angular polarization. The effects of the atomic cores are accounted for by means of pseudo-potential operators. Different atomic cores cause specific bond differences. The various bonding mechanisms can be characterized by several parameters. They describe the quantum-mechanical reduction in the 'electronic kinetic energy pressure' due to delocalization (sharing interference) and the increase in the 'molecular potential energy pull' due to overlap of atomic electron densities with adjacent atoms in the molecule. In addition, there are one- and two-electron relaxations whose distinctive features depend on the nature of the cores.
URL<Go to ISI>://000282508000015
DOI10.1007/S00214-010-0758-Y
Alternate JournalTheor Chem Acc