A new analysis of charge transfer and polarization for ligand-metal bonding - Model studies of Al4CO and Al4NH3

• Published in: The Journal of chemical physics 1984-05, Vol.80 (9), p.4378-4386
• Main Authors: Bagus, P. S., Hermann, K., Bauschlicher, C. W., Jr
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Effects of atomic and molecular interactions on electronic structure; Electronic structure of atoms, molecules and their ions: theory; Environmental and solvent effects; Exact sciences and technology; Inorganic And Physical Chemistry; Physics
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.447215

The nature of the bonding of CO and NH3 ligands to Al is analyzed, and the intra-unit charge polarization and inter-unit donation for the interaction of ligands with metals are studied. The consequences of metal-to-ligand and ligand-to-metal charge transfer are separately considered by performing a constrained space orbital variation (CSOV) with the electrons of the metal member of the complex in the field of frozen ligand. The electrons of the metal atoms are then frozen in the relaxed distribution given by the CSOV SCF wave function and the ligand electrons are allowed to relax. Quantitative measures of the importance of inter-unit charge transfers and intra-unit polarization are obtained using results of SCF studies of Al4CO and Al4NH3 clusters chosen to simulate the adsorption of the ligands at an on-top side of the Al(111) surface. The electrostatic attraction of the effective dipole moments of the metal and ligand units makes an important contribution to the bond.