s-Orbital mixing into d-orbital manifolds in complex compounds analyzed using Lowdin's orthogonalization procedure

摘要

Matrix elements calculated from valence orbital interactions between central metal and ligand orbitals considered by applying a (2nd order)perturbation procedure are used to investigate the s-d metal orbital mixing for different coordination.Depending on the geometry different degrees of intermixing are obtained.For a set of orthoazial MA_nB_(4-n)complexes,EHT orbital energies obtained from SCCC calculations agree very well with orbital stabilization energies for s-d mixing,predicted from the perturbation matrix elements.While s-d_z 2 intermixing is present at any coordination considered (except octahedral);s-d_x~2-_y~2 occurs only for MA_3B and trans[MA_2B_2]complexes,the latter to a significantly higher degree.