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How far do electrons delocalize?

Authors: Benjamin G, Janesko; Giovanni, Scalmani; Michael J, Frisch;

How far do electrons delocalize?

Abstract

Electron delocalization is central to chemical bonding, but it is also a fundamentally nonclassical and nonintuitive quantum mechanical phenomenon. Tools to quantify and visualize electron delocalization help to understand, teach, and predict chemical reactivity. We develop a new approach to quantify and visualize electron delocalization in real space. Our electron delocalization range function \documentclass[12pt]{minimal}\begin{document}${\textrm {EDR}}({\vec{r}};u)$\end{document} EDR (r⃗;u) quantifies the degree to which electrons at point \documentclass[12pt]{minimal}\begin{document}${\vec{r}}$\end{document}r⃗ in a calculated wavefunction delocalize over length scale u. Its predictions are physically reasonable. For example, \documentclass[12pt]{minimal}\begin{document}${\textrm {EDR}}({\vec{r}};u=0.25\ {\textrm {bohr}})$\end{document} EDR (r⃗;u=0.25 bohr ) is close to one at points \documentclass[12pt]{minimal}\begin{document}${\vec{r}}$\end{document}r⃗ in the cores of first-row atoms, consistent with the localization of core electrons to ∼0.25 bohr. \documentclass[12pt]{minimal}\begin{document}${\textrm {EDR}}({\vec{r}};u=1\ {\textrm {bohr}})$\end{document} EDR (r⃗;u=1 bohr ) is close to one at points \documentclass[12pt]{minimal}\begin{document}${\vec{r}}$\end{document}r⃗ in typical covalent bonds, consistent with electrons delocalizing over the length of the bond. Our approach provides a rich representation of atomic shell structure; covalent and ionic bonding; the delocalization of excited states, defects, and solvated electrons; metallic and insulating systems; and bond stretching and strong correlation.

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
39
Top 10%
Top 10%
Top 10%
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