Theoretical study of the mechanism of valence tautomerism in cobalt complexes

Daisuke Sato, Yoshihito Shiota, Gergely Juhász, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

38 引用 (Scopus)

抄録

Valence tautomerism is studied in the [CoII-HS(sq) 2(bpy)]/[CoIII-LS(sq)(cat)(bpy)] mononuclear cobalt complex by using DFT methods (HS, high spin; LS, low spin; cat, catecholate; sq, semiquinone; bpy, 2,2′-bipyridine). Calculations at the B3LYP* level of theory reproduce well the energy gap between the CoII-HS and CoIII-LS forms giving an energy gap of 4.4 kcal/mol, which is comparable to the experimental value of 8.9 kcal/mol. Potential energy surfaces and crossing seams of the electronic states of the doublet, quartet, and sextet spin states are calculated along minimum energy paths connecting the energy minima corresponding to the different spin states. The calculated minimum energy crossing points (MECPs) are located at 8.8 kcal/mol in the doublet/sextet surfaces, at 10.2 kcal/mol in the doublet/quartet surfaces, and at 8.4 kcal/mol in the quartet/sextet surfaces relative to the doublet ground state. Considering the energy of the three spin states and the crossing points, the one-step relaxation mechanism between the CoII-HS and CoIII-LS forms is the most probable. This research shows that mapping MECPs can be a useful strategy to analyze the potential energy surfaces of systems with complex deformation modes.

元の言語英語
ページ(範囲)12928-12935
ページ数8
ジャーナルJournal of Physical Chemistry A
114
発行部数49
DOI
出版物ステータス出版済み - 12 16 2010

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Cobalt
Potential energy surfaces
cobalt
valence
Energy gap
cats
Electronic states
Discrete Fourier transforms
Ground state
potential energy
energy
ground state
electronics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

これを引用

Theoretical study of the mechanism of valence tautomerism in cobalt complexes. / Sato, Daisuke; Shiota, Yoshihito; Juhász, Gergely; Yoshizawa, Kazunari.

:: Journal of Physical Chemistry A, 巻 114, 番号 49, 16.12.2010, p. 12928-12935.

研究成果: ジャーナルへの寄稿記事

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