Mechanism of photochemical reaction of permanganate ion

Hiromi Nakai, H. Nakatsuji

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The electronic mechanism of the photodecomposition reaction of MnO4 was investigated using an ab initio theory, taking into account electron correlation. The SAC (symmetry adapted cluster)/SAC-CI method was used to calculate the ground and excited states of the permanganate ion. It was found that to obtain reasonable descriptions of the ground and excited states of MnO4 , the inclusion of electron correlation is quite important. The experimental absorption spectrum of MnO4 was well reproduced by the present calculations. All the observed peaks were assigned to the electronic allowed transitions to the 1T2 excited states. We then calculated the potential-energy curves of the ground and excited states of MnO4 along the reaction pathway. The resulting potential-energy curves for the ground and excited states show that the excited 11A2 state plays a key role in the photochemical reaction. The energy barrier in the 11A2 state determines the strong wavelength dependence of the quantum yield and the slight temperature dependence at longer wavelengths. The electronic mechanism clarified by the present ab initio study is consistent with previously reported experimental results for the photochemical decomposition of MnO4 .

Original languageEnglish
Pages (from-to)141-151
Number of pages11
JournalJournal of Molecular Structure: THEOCHEM
Volume311
DOIs
Publication statusPublished - 1994 Jan 1
Externally publishedYes

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Photochemical reactions
Excited states
photochemical reactions
Ions
Ground state
excitation
Electron correlations
ions
ground state
Crystal symmetry
Potential energy
potential energy
electronics
Electrons
Wavelength
photodecomposition
Energy barriers
symmetry
Quantum yield
curves

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Mechanism of photochemical reaction of permanganate ion. / Nakai, Hiromi; Nakatsuji, H.

In: Journal of Molecular Structure: THEOCHEM, Vol. 311, 01.01.1994, p. 141-151.

Research output: Contribution to journalArticle

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abstract = "The electronic mechanism of the photodecomposition reaction of MnO4 − was investigated using an ab initio theory, taking into account electron correlation. The SAC (symmetry adapted cluster)/SAC-CI method was used to calculate the ground and excited states of the permanganate ion. It was found that to obtain reasonable descriptions of the ground and excited states of MnO4 −, the inclusion of electron correlation is quite important. The experimental absorption spectrum of MnO4 − was well reproduced by the present calculations. All the observed peaks were assigned to the electronic allowed transitions to the 1T2 excited states. We then calculated the potential-energy curves of the ground and excited states of MnO4 − along the reaction pathway. The resulting potential-energy curves for the ground and excited states show that the excited 11A2 state plays a key role in the photochemical reaction. The energy barrier in the 11A2 state determines the strong wavelength dependence of the quantum yield and the slight temperature dependence at longer wavelengths. The electronic mechanism clarified by the present ab initio study is consistent with previously reported experimental results for the photochemical decomposition of MnO4 −.",
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AB - The electronic mechanism of the photodecomposition reaction of MnO4 − was investigated using an ab initio theory, taking into account electron correlation. The SAC (symmetry adapted cluster)/SAC-CI method was used to calculate the ground and excited states of the permanganate ion. It was found that to obtain reasonable descriptions of the ground and excited states of MnO4 −, the inclusion of electron correlation is quite important. The experimental absorption spectrum of MnO4 − was well reproduced by the present calculations. All the observed peaks were assigned to the electronic allowed transitions to the 1T2 excited states. We then calculated the potential-energy curves of the ground and excited states of MnO4 − along the reaction pathway. The resulting potential-energy curves for the ground and excited states show that the excited 11A2 state plays a key role in the photochemical reaction. The energy barrier in the 11A2 state determines the strong wavelength dependence of the quantum yield and the slight temperature dependence at longer wavelengths. The electronic mechanism clarified by the present ab initio study is consistent with previously reported experimental results for the photochemical decomposition of MnO4 −.

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