Photoelectron Spectroscopy of Lanthanide−Silicon Cluster Anions LnSin− (3 ≤ n ≤ 13; Ln = Ho, Gd, Pr, Sm, Eu, Yb): Prospect for Magnetic Silicon-Based Clusters
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Abstract
Photoelectron spectroscopy was utilized to study a variety of LnSi(n)(-) cluster anions (Ln = Yb, Eu, Sm, Gd, Ho, Pr; 3 or= 10, adopt a nominal +2 oxidation state while Ho, Pr, Gd, and in case of Sm, sizes n <or= 7, exhibit a nominal +3 oxidation state. Furthermore, dramatic increases in adiabatic electron affinity values observed at n = 10 for the Ln(III)Si(n) series and at n = 12 for the Ln(II)Si(n) series were attributed to an inherent electronic stabilization of those particular clusters, rather than to the lanthanides' encapsulation. The observed limited effect of f-electrons on the valence electronic structure and thus on bonding in LnSi(n)(-) clusters may leave these electrons available for inducing magnetism. Consequently, Ln@Si(n) clusters may hold promise as building blocks of silicon-based cluster materials with magnetic properties.
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