The structures and chemical bond evolution of ditantalum doped carbon clusters Ta2Cn-/0 (n = 1-7) were studied via size-selected anion photoelectron spectroscopy and theoretical calculations. It is found that Ta2C-/0 has a triangular structure and Ta2C2-/0 has a quasi-rhombus structure with C2v symmetry. Ta2C3- has a quasi-planar structure with a carbon atom and a C2 unit interacting with two tantalum atoms, and the lowest-energy isomer of neutral Ta2C3 has a triangular bipyramid structure with three carbon atoms around the Ta2 unit. Ta2C4-/0 has two C2 units connected with the Ta2 unit in parallel. Two isomers of Ta2C5- are observed, where both isomers have one carbon atom and two C2 units bound to the Ta2 unit in different ways. The most stable structure of neutral Ta2C5 has one carbon atom added on top of the Ta2C4 cluster. The most stable structures of Ta2C6-7-/0 can be viewed as a C2 unit and a C3 unit capping a butterfly like Ta2C4 structure, respectively. Molecular orbital analysis shows that neutral Ta2C3 has a large gap between its highest occupied molecular orbital and lowest unoccupied molecular orbital. Chemical bonding analysis reveals that the Ta-Ta interactions in Ta2Cn-/0 (n = 1-7) clusters are slightly weaker than the Ta-Ta interaction in bare Ta2 due to the participation in forming multicenter bonds.
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