Q. Excited states of transition metal complexes

 

A. In our experiences, the following basis sets work very nicely for the excited states of tetraoxo-transition metal complexes and photochemistry of Ni(CO)₄.  Our recommendation is the valence double-zeta set plus double polarization p-function for the central metal and the double-zeta set for the ligand atoms. In Ni(CO)₄, [6s2p2d/4s2p] set was augmented with double polarization p-function for the Ni atom and with Rydberg s and p functions for the C and O atoms (J. Chem. Phys. 103, 6993-6998 (1995)). In TcO₄^2-, [7s3p3d/4s2p] set was augmented with double polarization p-function for the Tc atom (Theoret. Chim. Acta, 92, 351-359 (1995)). Please find more details in the original papers and the references therein. Use of ECP is not recommended (J. Chem. Phys., 97, 2561-2570 (1992)).