Theoretical study on the photochemical decomposition reaction of permanganate ion, MnO4-

Hiromi Nakai, Yutaka Ohmori, Hiroshi Nakatsuji

研究成果: Article査読

16 被引用数 (Scopus)

抄録

The electronic mechanism of the photodecomposition reaction of MnO4- is investigated. The symmetry-adapted cluster (SAC)/SAC-configuration interaction (SAC-CI) method is used for calculating the ground and excited states of the permanganate ion along the reaction pathway. Electron correlations are very important for reasonable descriptions of the ground and excited states. The 546- and 311-nm absorption bands, which lead to the photodecomposition reaction, are the dipole-allowed transitions to the 11T2 and 31T2 states, respectively. The lowest excited state plays a key role in the reaction. The decomposition leading to the ground state of the products, MnO2 -(3Δg+) + O2(3Σg-), occurs directly along the lowest-excited-state potential curve. The energy barrier existing in the lowest-excited-state curve is the origin of the strong wavelength dependence of the quantum yield and the slight temperature dependence at the longer wavelength region observed by Zimmerman (J. Chem. Phys. 1955, 23, 825). The photochemical and thermal decomposition reactions are shown to be symmetry allowed and forbidden, respectively. The peroxo complex in the 11A1 ground state corresponds to the long-lived intermediate observed experimentally. The electronic mechanism proposed by the present ab initia study slightly modifies and confirms the experimental reaction scheme (Scheme 1) given by Lee et al. (J. Am. Chem. Soc. 1987, 709, 3003).

本文言語English
ページ(範囲)8550-8555
ページ数6
ジャーナルJournal of physical chemistry
99
21
DOI
出版ステータスPublished - 1995 1 1
外部発表はい

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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