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

Hiromi Nakai, Yutaka Ohmori, Hiroshi Nakatsuji*


研究成果: Article査読

17 被引用数 (Scopus)


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).

ジャーナルJournal of physical chemistry
出版ステータスPublished - 1995 1月 1

ASJC Scopus subject areas

  • 工学(全般)
  • 物理化学および理論化学


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