The electronic structure of the heptafulvalene trianion radical—The doublet instability of the Hartree-Fock solution and related phenomena

Toyota, Azumao; Nakajima, Takeshi

doi:10.1007/bf02394730

Cited by 4 publications

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“…With regard to the distribution of the atomic-orbital coefficients in the two orbitals of interest, a quite similar situation can also be observed for the radicals 2 and 3 . As a consequence, it follows that the localization in unpaired spin density takes place in the C 2 v structure of the radicals 2 Representation of the Hückel SOMO (b 1g ) and LUMO (a u ) for the radical 1 at the D 2 h structure.…”

Section: Resultsmentioning

confidence: 95%

Energy Component Analysis of the Pseudo-Jahn−Teller Effect in the Ground State of the Triafulvalene Anion, Pentafulvalene Cation, and Heptafulvalene Anion Radicals

Toyota

Koseki

1998

J. Phys. Chem. A

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To understand the nature of the pseudo-Jahn−Teller (JT) effect, an energy component analysis of the total energy was carried out in the ground state of the titled ion radicals by using the MCSCF method with 6-31G(d) basis set. Examination of the energy components comprising in the total energy reveals that in the radicals the stability of a less symmetrical nuclear configuration (C 2 v ) is attributable commonly to the energy lowering of the internuclear repulsion term and the kinetic and interelectronic repulsion terms due to σ electrons. These observations are consistent with an expansion of the molecular skeleton brought about by the pseudo-JT distortion. In the triafulvalene anion radical, it is further found that the nuclear−electron attractive and interelectronic repulsive terms due to π electrons also contribute to the stability of the C 2 v structure. In the pentafulvalene cation and heptafulvalene anion radicals, on the other hand, the interelectronic repulsive and nuclear−electron attractive terms due to π electrons contribute to the stability of the C 2 v structure, respectively. These differences are accounted for in terms of a charge polarization attributed to the migration of π electrons. Moreover, characteristic electronic properties inherent in the radicals are discussed with much attention to the charge and unpaired spin-density distributions in the distorted C 2 v structure.

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Section: Resultsmentioning

confidence: 95%