Density Functional Study of Ferrocene, Cobaltocene and Nickelocene

Abstract: The electronic structure and geometry optimization of ferrocene, cobaltocene and nickelocene molecules using DFT/B3LYP with the basis set of 6-31G (d). The Eigen values, Eigen vector and population analysis of the molecules show that the first 13 molecular orbitals in ferrocene, 12 in cobaltocene and 14 in nickelocene have contribution from 2pz orbitals of carbon of (C5H5)¿ and 4s, 4p and 3d orbitals of iron, cobalt or nickel, respectively. The extent of involvement of metal orbitals in the three cases is different. In ferrocene the maximum involvement out of 4s and 4p orbitalis in the order 4pz > 4py > 4s > 4pxand out of 3d orbitals the order of involvement is 3dyz >3dxz >3d2z>3dx2¿y2 >3dxy. The involvement of corresponding orbital in cobaltocene with respect to the 4s and 4p orbitals is in the order of 4s > 4pz > 4py > 4px and in 3d orbitals the order is 3dx2¿y2 >3dxz> 3d2z > 3dx2¿y2 and 4py >4px >4s >4pzand in the nickelocene molecule it is 3dyz >3dx2¿y2 >3dxy >3dxz >3d2z. The total involvement of 3d, 4s and 4p orbitals of metal and 2pz orbitals of the ten carbon atoms of both ligands of (C5H5)¿.