配位子場分裂
It is well known that the d2sp3 type hybridized molecular orbital can be created by dx2-y2, dz2, s-orbital, and three p-orbitals in the six-coordinated octahedral metal complex. We calculated the electronic structure of the octahedral ML6 metal complex by means of molecular orbital calculation in order to compare and discuss the mechanism of the creation of molecular orbitals and a relationship with a d2sp3 type hybridized molecular orbital expected by a valence bond theory. The [FeCl6]3- molecule has been employed as a target material to calculate the electronic structure. In the compound the interatomic Fe-Cl distance has been reported to be 2.4 angstrom by a X-ray crystal structural analysis. The energy structures have been calculated by changing the interatomic Fe-Cl distance. The interatomic distance dependence of the three dimensional wave functions have been visualized in order to compare the molecular orbitals and an octahedral symmetrical d2sp3 hybridized molecular orbitals. From the result of the molecular orbital calculation, no octahedral symmetrical six orbitals have been found. We obtain the three dimensional electronic dispersion by a summation of six squared molecular orbitals. Therefore, we can reproduce the three dimensional total electron density consisting with the octahedral symmetrical molecular structure in ML6 complex.
