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The Description of Chemical Bonding From AB Initio Calculations

Goddard, William A., III and Harding, Lawrence B. (1978) The Description of Chemical Bonding From AB Initio Calculations. Annual Review of Physical Chemistry, 29 . pp. 363-396. ISSN 0066-426X. doi:10.1146/annurev.pc.29.100178.002051.

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Concepts, such as hybridization and electronegativity, developed by Linus Pauling (1), Robert Mulliken (2), John Slater (3), and others in the 1930s have been powerful in rationalizing and predicting molecular structure, bond energies, and some aspects of reactivity. The power of these concepts is exemplified in the classic exposition, Nature of the Chemical Bond, by Linus Pauling (4). In recent years experimental and theoretical studies of numerous radicals have provided an assembly of quantitative information concerning bond energies, excitation energies, relative ordering of states, and shapes of potential curves, much of which is not explained by the older ideas. However, it has recently become possible to abstract from ab initio calculations qualitative concepts that rationalize many of the observed properties in such a way as to allow quantitative predictions for related systems. Currently the basis and application of this approach is distributed over a number of papers (5-9). Here we draw these ideas together with applications to number of related systems so as to indicate the utility and force of these methods. For simplicity of presentation we use Si and its hydrides (SiH, SiH_2, SiH_3, SiH_4) as prototypes for outlining the various concepts. These ideas are then extended to other molecules by replacing Si with Be through F and Mg through C1, and other related nontransition metal elements, and by replacing H with halogens such as F and C1.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1978 Annual Reviews Inc. Contribution No. 5731. We thank Arthur F. Voter and Michael L. Steigerwald for supplying us with material related to their calculations on SiH and SiH_2, respectively. Acknowledgment is made to the Donors of The Petroleum Research Fund, administered by the American Chemical Society, and to the National Science Foundation (DMR74-04965) for partial support of this research.
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American Chemical Society Petroleum Research FundUNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics5731
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Official Citation:The Description of Chemical Bonding From AB Initio Calculations Annual Review of Physical Chemistry Vol. 29: 363-396 (Volume publication date October 1978)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32782
Deposited By: Ruth Sustaita
Deposited On:30 Jul 2012 17:09
Last Modified:09 Nov 2021 21:29

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