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

doi:10.1063/1.466275

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 journal › Article › peer-review

33 Citations (Scopus)

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 D_3h 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 D_3h geometry is predicted to lie well below the ²A₂ state with a planar C_2υ 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 D_3h 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 language	English
Pages (from-to)	4453-4458
Number of pages	6
Journal	The Journal of Chemical Physics
Volume	100
Issue number	6
DOIs	https://doi.org/10.1063/1.466275
Publication status	Published - Jan 1 1994
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Ab initio study on quartet states of non-Kekul{\'e}-type molecules 1,3,5-trimethylenebenzene and 1,3,5-triaminobenzene trication",

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.",

author = "Kazunari Yoshizawa and Masashi Hatanaka and Yoichi Matsuzaki and Kazuyoshi Tanaka and Tokio Yamabe",

year = "1994",

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T1 - Ab initio study on quartet states of non-Kekulé-type molecules 1,3,5-trimethylenebenzene and 1,3,5-triaminobenzene trication

AU - Yoshizawa, Kazunari

AU - Hatanaka, Masashi

AU - Matsuzaki, Yoichi

AU - Tanaka, Kazuyoshi

AU - Yamabe, Tokio

PY - 1994/1/1

Y1 - 1994/1/1

N2 - 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 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.

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

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