Theoretical study of the homonuclear tetramers and pentamers of the group IB metals (Cu, Ag, and Au)

Abstract

We find the optimal structures of the homonuclear tetramers and pentamers of Cu, Ag, and Au to be planar trapezoidal. However, on the basis of spin densities deduced from electron spin resonance experiments, it has been suggested that these pentamers have distorted trigonal bipyramidal structures. This apparent discrepancy is reconciled by the fact that Mulliken populational analyses indicate that the open-shell spin density distribution on the planar structures are also consistent with experiment. Since the vertical electron attachment energies for both the tetramers and pentamers are in good agreement with experiment, the negative ions probably also have planar trapezoidal structures. The trends in ionization potentials, atomization energies, and electron affinities with cluster size are discussed.