Equilibrium geometries, electronic structure and magnetic properties of small manganese clusters

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Abstract
The equilibrium geometries, electronic structure and magnetic properties of small Mn clusters consisting of up to five atoms have been calculated self-consistently using first principles molecular orbital theory. The electron-electron interaction has been accounted for using the local spin density and generalized gradient approximation to the density functional theory. The atomic orbitals forming the molecular orbital have been represented separately by Gaussian and numerical basis sets. Two different computer codes (Gaussian 94 and DMOL) were used to check the numerical consistency of our calculations. is found to be a weakly bound van der Waals molecule and its binding energy depends sensitively on the choice of basis set as well as the form of the exchange-correlation potential. The binding energies are less sensitive to these approximations in larger clusters. The binding improves with cluster size, but remains significantly lower than those in other transition metal clusters. The equilibrium geometries are fairly compact and symmetric although other isomers with distorted geometries and with nearly the same energy as that of the ground state do exist for . The clusters also exhibit a variety of low-lying spin multiplicities, but the ground state spin configuration is ferromagnetic with a magnetic moment of . This not only contrasts with its bulk behaviour which is antiferromagnetic, but also differs from the behaviour in other transition-metal clusters where the magnetic moments/atom are always less than the free-atom value. The results are compared with available experiments on matrix isolated Mn clusters.