Electronic structure and properties of transition metal-benzene complexes

A comprehensive theoretical study of the geometries, energetics, and electronic structure of neutral and charged 3d transition metal atoms (M) interacting with benzene molecules (Bz) is carried out using density functional theory and generalized gradient approximation for the exchange-correlation potential. The variation of the metal-benzene distances, dissociation energies, ionization potentials, electron affinities, and spin multiplicities across the 3d series in MBz complexes differs qualitatively from those in M(Bz)2. For example, the stability of Cr(Bz)2 is enhanced over that of CrBz by almost a factor of 30. On the other hand, the magnetic moment of Cr(Bz)2 is completely quenched although CrBz has the highest magnetic moment, namely 6μB, in the 3d metal-benzene series. In multidecker complexes involving V2(Bz)3 and Fe2(Bz)3, the metal atoms are found to couple antiferromagnetically. In addition, their dissociation energies and ionization potentials are reduced from those in corresponding M(Bz)2 complexes. All of these results agree well with available experimental data and demonstrate the important role the organic support can play on the properties of metal atoms/clusters