Theoretical study on the ground and excited states of MnO4 -

Hiromi Nakai, Yutaka Ohmori, Hiroshi Nakatsuji

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

The symmetry adapted cluster (SAC) and SAC-configuration interaction (SAC-CI) theories are applied to the calculations of the ground and excited states of MnO4 -. With the use of three different active spaces, we examine the convergence of the results. Electron correlations work to relax charge polarizations of the Mn-O bonds in the ground state. The experimental spectrum of MnO4 - is well reproduced by the present calculations. All of the observed peaks are assigned to the electronic allowed transitions to the 1T2 excited states. They are characterized as the excitations from the nonbonding Orbitals of oxygen to the antibonding orbitals between the metal and oxygens. For reasonable descriptions of the ground and excited states of MnO4 -, electron correlations should be considered with the use of large enough active space for expressing the relaxations of valence electrons. In this sense, all of the previous theoretical assignments of the spectra are unreliable, since they are not the results of calculations including sufficient amount of electron correlations.

Original languageEnglish
Pages (from-to)8287-8291
Number of pages5
JournalJournal of Chemical Physics
Volume95
Issue number11
Publication statusPublished - 1991
Externally publishedYes

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Electron correlations
Excited states
Ground state
ground state
Oxygen
excitation
electrons
Crystal symmetry
Electron transitions
orbitals
symmetry
oxygen
Metals
Polarization
configuration interaction
Electrons
valence
permanganic acid
polarization
electronics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Theoretical study on the ground and excited states of MnO4 - . / Nakai, Hiromi; Ohmori, Yutaka; Nakatsuji, Hiroshi.

In: Journal of Chemical Physics, Vol. 95, No. 11, 1991, p. 8287-8291.

Research output: Contribution to journalArticle

Nakai, H, Ohmori, Y & Nakatsuji, H 1991, 'Theoretical study on the ground and excited states of MnO4 - ', Journal of Chemical Physics, vol. 95, no. 11, pp. 8287-8291.
Nakai, Hiromi ; Ohmori, Yutaka ; Nakatsuji, Hiroshi. / Theoretical study on the ground and excited states of MnO4 - In: Journal of Chemical Physics. 1991 ; Vol. 95, No. 11. pp. 8287-8291.
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