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

Hiromi Nakai, Yutaka Ohmori, Hiroshi Nakatsuji

Research output: Contribution to journalArticle

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Abstract

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).

Original languageEnglish
Pages (from-to)8550-8555
Number of pages6
JournalJournal of Physical Chemistry
Volume99
Issue number21
Publication statusPublished - 1995
Externally publishedYes

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Excited states
Ground state
Ions
Decomposition
decomposition
photodecomposition
ions
ground state
excitation
symmetry
Electron correlations
Wavelength
Energy barriers
Quantum yield
curves
Absorption spectra
electronics
Pyrolysis
wavelengths
configuration interaction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical study on the photochemical decomposition reaction of permanganate ion, MnO4 - . / Nakai, Hiromi; Ohmori, Yutaka; Nakatsuji, Hiroshi.

In: Journal of Physical Chemistry, Vol. 99, No. 21, 1995, p. 8550-8555.

Research output: Contribution to journalArticle

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AB - 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).

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