RESUMO
The geometric and electronic structures of a small series of mixed gold and platinum AuxPty2+ clusters, with x + y = 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 y = 5. This affects the clusters' electron population, chemical bonding, and stability. For the Pt-doped Au clusters with y values from 2 to 5, the bonds enable Pt atoms to assemble into symmetric line, triangle, quadrangle, and tetragonal pyramidal Pty blocks, respectively. For the Au-doped Pt clusters, with larger values of y > 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 Pt102+ at y = 10 exhibiting the highest stability. While the ground electronic state of the neutral platinum atom [Xe]. 4f145d96s1 leads to a triplet state (3D3), the total magnetic moments of AuxPty2+ are large increasing steadily from 0 to 10 µB 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.
RESUMO
A series of small chromium-doped silicon clusters CrSin with n = 3-10 in the cationic, neutral and anionic charge states were investigated using quantum chemical methods. The CrSin+ cations with n = 6-10 were produced in the gas phase and characterized by far-IR multiple photon dissociation (IR-MPD) spectroscopy. Good agreement between experimental spectra in the 200-600 cm-1 frequency range and those determined for the lowest-energy isomers by density functional theory calculations (B3P86/6-311+G(d)) provide a strong support for the geometrical assignments. An extensive structural comparison for the three different charge states shows that the structural growth mechanism inherently depends on the charge. While the structures of the cationic clusters are preferentially formed by addition of the Cr dopant to the corresponding pure silicon cluster, it favors substitution in both the neutral and anionic counterparts. The Si-Cr bonds of the studied CrSin+/0/- clusters are polar covalent. Apart from a basket-like Cr@Si9- and an endohedral Cr@Si10- cage, the Cr dopant takes an exohedral position and bears a large positive charge in the clusters. The exohedrally doped clusters also have a high spin density on Cr, manifesting the fact that the intrinsic magnetic moment of the transition metal dopant is well conserved. Three CrSin clusters have a pair of enantiomeric isomers in their ground state, namely the cationic n = 9 and the neutral and anionic n = 7. Those can be distinguished from each other by their electronic circular dichroism spectra, calculated using time-dependent density functional theory. Those enantiomers, being intrinsically chiral inorganic compounds, might be used as building blocks of optical-magnetic nanomaterials because of their high magnetic moments and ability to rotate the plane of polarization.