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Cyclobutadiene radical cation. An ab initio study of the Jahn-Teller surface

✍ Scribed by Martina Roeselová; Thomas Bally; Pavel Jungwirth; Petr Čársky

Publisher: Elsevier Science
Year: 1995
Tongue: English
Weight: 706 KB
Volume: 234
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(94)00056-v

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✦ Synopsis

The Jahn-Teller potential energy surface of the cyclobutadiene radical cation is reinvestigated at the CCSD(T)/TZP//RMP2/6-311G(2d, p) level. It is found that out-of-plane deformations come into play as one moves away from the Dab geometry. The relaxed radical cation has two potential energy minima, a planar rectangle 1.7 kcal/mol below a puckered rhombus, which are interconnected by a transition state lying 1.5 kcal/mol above the latter. However, upon inclusion of zero-point energies, the transition state falls 0.1 kcal/mol below the puckered minimum and the enthalpies at 0 K of the three stationary points all lie within 0.54 kcal/mol. This indicates that the potential energy surface of this cation is strongly anharmonic. The repercussions of these findings with regard to recent experiments are discussed.

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