Ab initio study on quartet states of non-Kekulé-type molecules 1,3,5-trimethylenebenzene and 1,3,5-triaminobenzene trication

Kazunari Yoshizawa, Masashi Hatanaka, Yoichi Matsuzaki, Kazuyoshi Tanaka, Tokio Yamabe

Research output: Contribution to journalArticle

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Abstract

The electronic structures of non-Kekulé-type isoelectronic molecules 1,3,5-trimethylenebenzene (TMB) and 1,3,5-triaminobenzene trication (TAB 3+) having a threefold axis are discussed with the ab initia molecular orbital (MO) method. The quartet state with a D3h geometry is predicted to be the ground state of TMB and TAB3+. According to the Jahn-Teller theorem, the doublet 2E″ states of TMB and TAB3+ are subject to the first order distortions which remove the degeneracy. The quartet-doublet energy splittings are calculated for these non-Kekulé-type molecules at the second order Møller-Plesset (MP2) perturbation level of theory. In TMB the 4A″2 state with a planar D3h geometry is predicted to lie well below the 2A2 state with a planar C geometry in which one of the methylene groups has a longer C-C bridge bond connecting with the benzene ring. Moreover, in TAB3+ the 4A″ 2 state with a planar D3h geometry also lies well below the 2A2 state. The 2A2- 2B1 energy splittings on the pseudorotation potential surface overestimated at the unrestricted Hartree-Fock (UHF) level are corrected with the MP2 method.

Original languageEnglish
Pages (from-to)4453-4458
Number of pages6
JournalThe Journal of Chemical Physics
Volume100
Issue number6
DOIs
Publication statusPublished - Jan 1 1994

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Molecules
Geometry
geometry
molecules
Molecular orbitals
Benzene
methylene
Ground state
Electronic structure
molecular orbitals
theorems
benzene
electronic structure
perturbation
ground state
1,3,5-trimethylenebenzene
energy
rings

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Ab initio study on quartet states of non-Kekulé-type molecules 1,3,5-trimethylenebenzene and 1,3,5-triaminobenzene trication. / Yoshizawa, Kazunari; Hatanaka, Masashi; Matsuzaki, Yoichi; Tanaka, Kazuyoshi; Yamabe, Tokio.

In: The Journal of Chemical Physics, Vol. 100, No. 6, 01.01.1994, p. 4453-4458.

Research output: Contribution to journalArticle

Yoshizawa, Kazunari ; Hatanaka, Masashi ; Matsuzaki, Yoichi ; Tanaka, Kazuyoshi ; Yamabe, Tokio. / Ab initio study on quartet states of non-Kekulé-type molecules 1,3,5-trimethylenebenzene and 1,3,5-triaminobenzene trication. In: The Journal of Chemical Physics. 1994 ; Vol. 100, No. 6. pp. 4453-4458.
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abstract = "The electronic structures of non-Kekul{\'e}-type isoelectronic molecules 1,3,5-trimethylenebenzene (TMB) and 1,3,5-triaminobenzene trication (TAB 3+) having a threefold axis are discussed with the ab initia molecular orbital (MO) method. The quartet state with a D3h geometry is predicted to be the ground state of TMB and TAB3+. According to the Jahn-Teller theorem, the doublet 2E″ states of TMB and TAB3+ are subject to the first order distortions which remove the degeneracy. The quartet-doublet energy splittings are calculated for these non-Kekul{\'e}-type molecules at the second order M{\o}ller-Plesset (MP2) perturbation level of theory. In TMB the 4A″2 state with a planar D3h geometry is predicted to lie well below the 2A2 state with a planar C2υ geometry in which one of the methylene groups has a longer C-C bridge bond connecting with the benzene ring. Moreover, in TAB3+ the 4A″ 2 state with a planar D3h geometry also lies well below the 2A2 state. The 2A2- 2B1 energy splittings on the pseudorotation potential surface overestimated at the unrestricted Hartree-Fock (UHF) level are corrected with the MP2 method.",
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