Formation of pyramidal structures through mixing gold and platinum atoms: the AuPt clusters with + = 10.

The geometric and electronic structures of a small series of mixed gold and platinum AuPt clusters, with + = 10, were investigated using quantum chemical methods. A consistent tetrahedral pyramid structure emerges, displaying two patterns of structural growth by a notable critical point at = 5. This affects the clusters' electron population, chemical bonding, and stability. For the Pt-doped Au clusters with values from 2 to 5, the bonds enable Pt atoms to assemble into symmetric line, triangle, quadrangle, and tetragonal pyramidal Pt blocks, respectively. For the Au-doped Pt clusters, with larger values of > 5, the structures are more relaxed and the d electrons of Pt atoms become delocalized over more centers, leading to lower symmetry structures. A certain aromaticity arising from delocalization of d electrons over the multi-center framework in the doped Pt clusters contributes to their stability, with Pt at = 10 exhibiting the highest stability. While the ground electronic state of the neutral platinum atom [Xe]. 4f5d6s leads to a triplet state (D), the total magnetic moments of AuPt are large increasing steadily from 0 to 10 and primarily located on Pt atoms, corresponding to the increase of the number of Pt atoms from 0 to 10 and significantly enhancing the magnetic moments. An admixture of both Au and Pt atoms thus emerges as an elegant way of keeping a small pyramidal structure but bringing in a high and controllable magnetic moment.