Tetraoxo-metal complexes

Various kinds of the theoretical spectroscopies for the transition metal complexes were also reviewed. For the excitation spectrum of Cr02Cl2, the SAC-Cl method simulated accurate spectrum. For tetraoxo metal complexes, the systematic studies explained the spectral differences when the central metal was substituted. In the analysis of the NMR chemical shift, not only the optically allowed states but also the magnetically allowed states are important. In the molybdenum complexes, the inverse of the d-d excitation energy is proportional to the experimental chemical shift. The photofragmentation reaction of Ni(CO)4 was also studied and the reaction mechanism was clarified. 

Fig. 39.12 summarizes the SAC-CI spectra for the lowest three excited states of six tetraoxo complexes. The SAC-CI calculations were the first applications that successfully reproduced the experimental absorption spectra of the transition metal complexes. The singly excited Cl (SECI) [97] and Xa [98] calculations often gave even qualitatively... 

Fig. 39.12. The lowest three excited states of the tetraoxo transition metal complexes. The dotted lines show the...

Stiickl, A.C., Daul, C.A., and Giidel, H.U. Excited-state energies and distortions of d(0) transition metal tetraoxo complexes A density functional study. J. Chem. Phys. 1997,107,4606 617. 

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