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A series of silicon clusters containing four atoms but with different charge states (Si4(2+), Si4, Si4(2-), and NaSi4-) were studied by photoelectron spectroscopy and ab initio calculations. Structure evolution and chemical bonding in this series were interpreted in terms of aromaticity and antiaromaticity, which allowed the prediction of how structures of the four-atom silicon clusters change upon addition or removal of two electrons. It is shown that Si4(2+) is square-planar, analogous to the recently discovered aromatic Al4(2-) cluster.

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