Anion photoelectron spectroscopy and quantum chemistry calculations of TaSi16-/0 clusters: global minimum fullerene-like cage structure, bonding and superatom properties

Anion photoelectron spectroscopy combined with quantum chemistry calculations and a particle swarm optimization (CALYPSO) global search algorithm were used to investigate the structural and bonding properties of TaSi16-/0 clusters. The vertical detachment energy (VDE) of TaSi16- was measured to be 3.81 +/- 0.08 eV. The global minima of the TaSi16- anion and TaSi16 neutral are confirmed to be a fullerene-like cage structure with the central Ta atom coordinated with nine Si atoms. Molecular orbital analysis shows that TaSi16- possesses sigma + pi double delocalized bonding patterns and has a large HOMO-LUMO gap. TaSi16- can be viewed as a superatom cluster due to the closed-shell electron configuration of |1S(2)|1P(6)|1D(10)|2S(2)|1F(14)|2P(6)|2D(10)|1G(18)|3S(2)| in terms of the jellium model. Theoretical calculations indicate that both the TaSi16- anion and TaSi16 neutral have aromaticity.

Automated summary

Anion photoelectron spectroscopy, quantum chemistry calculations, and a particle swarm optimization algorithm were used to investigate the structural and bonding properties of TaSi16-/0 clusters. The results showed that both the TaSi16- anion and TaSi16 neutral have a fullerene-like cage structure with double delocalized bonding patterns and aromaticity. TaSi16- was also identified as a superatom cluster with a closed-shell electron configuration.