Atomic clusters containing from two to several hundred atoms offer the possibility of studying the transition from molecules to crystalline solids. The covalent group IV elements carbon, silicon, and germanium are now being examined with this long-range objective. These elements are particularly interesting because of the very different character of their crystalline solids and because they are intermediate between metals and insulators in the nature of their bonding. Small mass-selected atom cluster ions are formed by pulsed laser techniques and identified by time-of-flight methods. Laser photoexcitation is used to study the relative stability of these clusters and their modes of fragmentation. These modes for C n + clusters, which tend to fragment with a characteristic loss of a neutral C 3 , are found to be different from the modes for Si n + and Ge n + clusters, which tend to fragment to "magic" clusters such as Si 4 + , Si 6 + and Si 10 + . These experimental results can be accounted for by recent theoretical calculations of the ground-state structure and stability of small silicon and carbon clusters. Several theoretical approaches give consistent results, showing that small silicon clusters are compact and different from small fragments of the bulk crystal. Calculations show that carbon clusters change from linear structures toward cyclic structures as the cluster size increases, but with significant odd-even differences.

Brown, W. L., Freeman, R. R., Raghavachari, K., & Schlüter, M. (1987). Covalent Group IV Atomic Clusters. Science, 235(4791), 860–865.