A valence bond analysis of electronic degeneracies in Jahn-Teller systems: Low-lying states of the cyclopentadienyl radical and cation

Shmuel Zilberg; Yehuda Haas

doi:10.1021/ja026304y

A valence bond analysis of electronic degeneracies in Jahn-Teller systems: Low-lying states of the cyclopentadienyl radical and cation

Shmuel Zilberg, Yehuda Haas

Research output: Contribution to journal › Article › peer-review

39 Scopus citations

Abstract

The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D_5h structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.

Original language	English
Pages (from-to)	10683-10691
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	124
Issue number	36
DOIs	https://doi.org/10.1021/ja026304y
State	Published - 11 Sep 2002
Externally published	Yes

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abstract = "The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D5h structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.",

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N2 - The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D5h structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.

AB - The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D5h structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.

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A valence bond analysis of electronic degeneracies in Jahn-Teller systems: Low-lying states of the cyclopentadienyl radical and cation

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