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Issue 46, 2011
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How do electron localization functions describe π-electron delocalization?

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Abstract

Scalar fields provide an intuitive picture of chemical bonding. In particular, the electron localization function (ELF) has proven to be highly valuable in interpreting a broad range of bonding patterns. The discrimination between enhanced or reduced electron (de)localization within cyclic π-conjugated systems remains, however, challenging for ELF. In order to clearly distinguish between the local properties of ten highly and weakly π-(de)localized prototype systems, we compare the ELFs of both the canonical wave functions and electron-localized states (diabatic) with those of two closely related scalar fields: the electron localizability indicator (ELI-D) and the localized orbital locator (LOL). The simplest LOL function distinguishes enhanced from weak π-(de)localization in an insightful and reliable manner. LOL offers the finest contrast between annulenes with 4n/4n + 2 π electrons and their inorganic analogues as well as between hyperconjugated cyclopentadiene derivatives. LOLπ also gives an appealing and intuitive picture of the π-bond. In contrast, the most popular ELF fails to capture subtle contrasting local electronic properties and suffers from the arbitrariness of the σ/π dissection. The orbital separation of the most recent ELI-D is clear-cut but the interpretations sometime less straightforward in the present context.

Graphical abstract: How do electron localization functions describe π-electron delocalization?

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Publication details

The article was received on 05 Apr 2011, accepted on 13 May 2011 and first published on 09 Jun 2011


Article type: Paper
DOI: 10.1039/C1CP21055F
Phys. Chem. Chem. Phys., 2011,13, 20584-20592

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    How do electron localization functions describe π-electron delocalization?

    S. N. Steinmann, Y. Mo and C. Corminboeuf, Phys. Chem. Chem. Phys., 2011, 13, 20584
    DOI: 10.1039/C1CP21055F

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