Title: Disparate effects of Cu and V on structures of exohedral transition metal-doped silicon clusters: a combined far-infrared spectroscopic and computational study
Authors: Vu Thi, Ngan
Gruene, Philipp
Claes, Pieterjan
Janssens, Ewald
Fielicke, André
Nguyen, Minh Tho ×
Lievens, Peter #
Issue Date: Nov-2010
Series Title: Journal of the American Chemical Society vol:132 issue:44 pages:15589-15602
Abstract: The growth mechanisms of small cationic silicon clusters containing up to 11 Si atoms, exohedrally doped by V and Cu atoms, are described. We find that as dopants, V and Cu follow two different paths: while V prefers substitution of a silicon atom in a highly coordinated position of the cationic bare silicon clusters, Cu favors adsorption to the neutral or cationic bare clusters in a lower coordination site. The different behavior of the two transition metals becomes evident in the structures of Si(n)M(+) (n = 4-11 for M = V, and n = 6-11 for M = Cu), which are investigated by density functional theory and, for several sizes, confirmed by comparison with their experimental vibrational spectra. The spectra are measured on the corresponding Si(n)M(+)·Ar complexes, which can be formed for the exohedrally doped silicon clusters. The comparison between experimental and calculated spectra indicates that the BP86 functional is suitable to predict far-infrared spectra of these clusters. In most cases, the calculated infrared spectrum of the lowest-lying isomer fits well with the experiment, even when various isomers and different electronic states are close in energy. However, in a few cases, namely Si(9)Cu(+), Si(11)Cu(+), and Si(10)V(+), the experimentally verified isomers are not the lowest in energy according to the density functional theory calculations, but their structures still follow the described growth mechanism. The different growth patterns of the two series of doped Si clusters reflect the role of the transition metal's 3d orbitals in the binding of the dopant atoms.
ISSN: 0002-7863
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
Solid State Physics and Magnetism Section
× corresponding author
# (joint) last author

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