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

被引：38

作者：

Zilberg, S

Haas, Y ^{[1
]}

机构：

[1] Hebrew Univ Jerusalem, Dept Phys Chem, IL-91904 Jerusalem, Israel

[2] Hebrew Univ Jerusalem, FArkas Ctr Light Induced React, IL-91904 Jerusalem, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 36期

关键词：

D O I：

10.1021/ja026304y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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-sh 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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页码：10683 / 10691

页数：9

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[1] Solvolytic generation of antiaromatic cyclopentadienyl cations [J].

Allen, AD ;

Sumonja, M ;

Tidwell, TT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (10) :2371-2375

[2]

[Anonymous], 1982, ELECT CHEM REACTIONS

[3] The Jahn-Teller and related effects in the cyclopentadienyl radical.: II.: Vibrational analysis of the (A)over-tilde 2A2"- (X)over-tilde 2E1" electronic transition [J].

Applegate, BE ;

Bezant, AJ ;

Miller, TA .

JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (11) :4869-4882

[4] The Jahn-Teller and related effects in the cyclopentadienyl radical.: I.: The ab initio calculation of spectroscopically observable parameters [J].

Applegate, BE ;

Miller, TA ;

Barckholtz, TA .

JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (11) :4855-4868

[5] THE PHOTOLYSIS OF CYCLOPENTADIENYL COMPOUNDS OF TIN AND MERCURY - ELECTRON-SPIN RESONANCE-SPECTRA AND ELECTRONIC CONFIGURATION OF THE CYCLOPENTADIENYL, DEUTERIOCYCLOPENTADIENYL, AND ALKYLCYCLOPENTADIENYL RADICALS [J].

BARKER, PJ ;

DAVIES, AG ;

TSE, MW .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1980, (06) :941-948

[6] A CASSCF study of the cyclopentadienyl radical: conical intersections and the Jahn-Teller effect [J].

Bearpark, MJ ;

Robb, MA ;

Yamamoto, N .

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1999, 55 (03) :639-646

[7] Modern aspects of the Jahn-Teller effect theory and applications to molecular problems [J].

Bersuker, IB .

CHEMICAL REVIEWS, 2001, 101 (04) :1067-1114

[8]

BERSUKER IB, 1996, VIBRONIC INTERACTION

[9] POTENTIAL SURFACES FOR THE PLANAR CYCLOPENTADIENYL RADICAL AND CATION [J].

BORDEN, WT ;

DAVIDSON, ER .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (14) :3771-3775

[10] ISOTOPE EFFECTS IN ELECTRON SPIN RESONANCE - NEGATIVE ION OF CYCLO-OCTATETRAENE-1-D [J].

CARRINGTON, A ;

LONGUETH.HC ;

MOSS, RE ;

TODD, PF .

MOLECULAR PHYSICS, 1965, 9 (02) :187-+

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