A new class of silicon-carbon clusters: a full study of the hydrogenated SinC2H2, n=3,4,5, clusters in comparison with their isoelectronic carboranes C2BnHn+2

The structural and electronic characteristics of the Si(n)C(2)H(2), n=3,4,5, clusters are studied by ab initio calculations based on coupled cluster and density functional theory using the hybrid B3LYP functional. It is demonstrated that all three clusters are structurally and electronically homologous to the corresponding isoelectronic organometallic carboranes C(2)B(n)H(n+2). This homology, which is in full agreement with the analogy of Si(6) (2-) and B(6)H(6) (2-) demonstrated recently by the author J. Chem. Phys. 127, 014314 (2007)], includes not only the ground states but also the lower-lying isomers as well. These lowest lying isomers can be obtained by ortho, para, and meta substitutions from the corresponding Si(n) (2-), n=3,4,5, dianions. The energetic ordering of the low-lying isomers is in full agreement with the known valence and topological charge stability rules developed for carboranes. The hydrogenated clusters are much more stable than their nonhydrogenated counterparts. It is suggested that Si(3)C(2)H(2), Si(4)C(2)H(2), and Si(5)C(2)H(2), which can be probably found in interstellar space, are special examples of a general class of silicon-carbon clusters of the form Si(n)C(2)H(2), with analogous properties and similarities to the corresponding carboranes C(2)B(n)H(n+2). It is furthermore illustrated that the lowest energy structures of the Si(n)C(2) clusters can be obtained through a systematic and straightforward procedure from the Si(n)C(2)H(2) clusters. The present results could hopefully make possible the exploitation of the rich borane and carborane chemistry for the design and development of novel silicon and silicon-carbon composite nanomaterials.