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Electronic Stress as a Guiding Force for Chemical Bonding

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Electronic Effects in Organic Chemistry

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 351))

Abstract

In the electron-preceding picture of chemical change, the paramount problem is identifying favorable changes in electronic structure. The electronic stress tensor provides this information; its eigenvectors represent electronic normal modes, pointing the way towards energetically favorable (or unfavorable) chemical rearrangements. The resulting method is well founded in both density functional theory and the quantum theory of atoms in molecules (QTAIM). Stress tensor analysis is a natural way to extend the QTAIM to address chemical reactivity. The definition and basic properties of the electronic stress tensor are reviewed and the inherent ambiguity of the stress tensor is discussed. Extending previous work in which the stress tensor was used to analyze hydrogen-bonding patterns, this work focuses on chemical bonding patterns in organic reactions. Other related material (charge-shift bonding, links to the second-density-derivative tensor) is summarized and reviewed. The stress tensor provides a multifaceted characterization of bonding and can be used to predict and describe bond formation and migration.

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Acknowledgments

PWA thanks the Canada Research Chairs and NSERC for funding. Computational facilities were provided by Sharcnet. AG-G was supported by a fellowship from CONACYT (Mexico). The Knowledge Foundation (grant number 2004/0284) and the Hundred Talents Foundation of Hunan Province are gratefully acknowledged for the support of SJ and SRK. EE and ATL acknowledge financial support from Fondecyt through project No. 1090460

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada

    Alfredo Guevara-García & Paul W. Ayers

  2. College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China

    Samantha Jenkins & Steven R. Kirk

  3. Department of Engineering, University West, Trollhättan, 461 29, Sweden

    Samantha Jenkins & Steven R. Kirk

  4. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile

    Eleonora Echegaray & Alejandro Toro-Labbe

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  1. Alfredo Guevara-García
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  2. Paul W. Ayers
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  3. Samantha Jenkins
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  4. Steven R. Kirk
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  6. Alejandro Toro-Labbe
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Correspondence to Paul W. Ayers .

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  1. Universität Bonn, Institut für Physikalische und Theoretische Chemie, Bonn

    Barbara Kirchner

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Guevara-García, A., Ayers, P.W., Jenkins, S., Kirk, S.R., Echegaray, E., Toro-Labbe, A. (2011). Electronic Stress as a Guiding Force for Chemical Bonding. In: Kirchner, B. (eds) Electronic Effects in Organic Chemistry. Topics in Current Chemistry, vol 351. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2011_193

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