Vibronic interaction in metalloporphyrin π-anion radicals

Kazunari Yoshizawa, Tomonori Nakayama, Takashi Kamachi, Pawel M. Kozlowski

研究成果: ジャーナルへの寄稿記事

10 引用 (Scopus)

抄録

The vibronic (vibrational-electronic) interactions in the π-anion radicals of the metalloporphyrins (M=Cr, Mn, Fe, Co, Ni, Cu, and Zn), which show delocalized D4h structures in the neutral states, are discussed using B3LYP density-functional-theory calculations. The B1g and B2g modes of vibration can remove the degenerate 2E g state of the π-anion radicals in the D4h symmetric structures to lead to rectangular and diamond D2h distortions, respectively. Calculated vibronic coupling constants demonstrate that the Big modes of vibration better couple with the degenerate electronic state, leading to the rectangular D2h distortion. In particular, the Big modes of v10 and v11, which have dominant contributions from C α-Cm and Cβ-Cβ stretching, give large vibronic coupling constants in the π-anion radicals. The vibronic coupling constant can be viewed as the Jahn-Teller distortion force, and therefore these C-C stretching B1g modes will play a central role in the Jahn-Teller effect of the π-anion radicals of the metalloporphyrins.

元の言語英語
ページ(範囲)852-857
ページ数6
ジャーナルJournal of Physical Chemistry A
111
発行部数5
DOI
出版物ステータス出版済み - 2 8 2007

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Metalloporphyrins
Anions
anions
Jahn-Teller effect
electronics
Stretching
interactions
vibration mode
Diamond
Electronic states
Density functional theory
diamonds
density functional theory

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

これを引用

Vibronic interaction in metalloporphyrin π-anion radicals. / Yoshizawa, Kazunari; Nakayama, Tomonori; Kamachi, Takashi; Kozlowski, Pawel M.

:: Journal of Physical Chemistry A, 巻 111, 番号 5, 08.02.2007, p. 852-857.

研究成果: ジャーナルへの寄稿記事

Yoshizawa, Kazunari ; Nakayama, Tomonori ; Kamachi, Takashi ; Kozlowski, Pawel M. / Vibronic interaction in metalloporphyrin π-anion radicals. :: Journal of Physical Chemistry A. 2007 ; 巻 111, 番号 5. pp. 852-857.
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