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    Toward an Experimental Quantum Chemistry: Exploring a New Energy Partitioning
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    Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2015, 137, 32, 10282–10291
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    https://doi.org/10.1021/jacs.5b05600
    Published July 20, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    Following the work of L. C. Allen, this work begins by relating the central chemical concept of electronegativity with the average binding energy of electrons in a system. The average electron binding energy, χ̅, is in principle accessible from experiment, through photoelectron and X-ray spectroscopy. It can also be estimated theoretically. χ̅ has a rigorous and understandable connection to the total energy. That connection defines a new kind of energy decomposition scheme. The changing total energy in a reaction has three primary contributions to it: the average electron binding energy, the nuclear–nuclear repulsion, and multielectron interactions. This partitioning allows one to gain insight into the predominant factors behind a particular energetic preference. We can conclude whether an energy change in a transformation is favored or resisted by collective changes to the binding energy of electrons, the movement of nuclei, or multielectron interactions. For example, in the classical formation of H2 from atoms, orbital interactions dominate nearly canceling nuclear–nuclear repulsion and two-electron interactions. While in electron attachment to an H atom, the multielectron interactions drive the reaction. Looking at the balance of average electron binding energy, multielectron, and nuclear–nuclear contributions one can judge when more traditional electronegativity arguments can be justifiably invoked in the rationalization of a particular chemical event.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b05600.

    • Demonstration of χ̅ from canonical and localized orbitals. Discussion on how to calculate χ̅ for extended systems. Dependence of χ̅ on the level of theory and basis set. Python code for performing the χ̅-analysis (PDF)

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    Cite this: J. Am. Chem. Soc. 2015, 137, 32, 10282–10291
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.5b05600
    Published July 20, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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