Photoelectron Spectroscopy and Theoretical Studies on the Structures and Properties of Ge₄C^– and Ge₄CH^– Clusters

We investigate the structures and properties of Ge₄C^-/0 and Ge₄CH^-/0 clusters using anion photoelectron spectroscopy and theoretical calculations. Our calculations show that the first two low-lying isomers coexist in the experiments of Ge₄C^- and Ge₄CH^-. The first two low-lying isomers of Ge₄C^- have trigonal bipyramidal structures with the C atom on the equatorial plane and the top vertex, respectively. It is found that the first two low-lying isomers of Ge₄CH^- can be obtained by adding an H atom to the top and equatorial C atoms of Ge₄C^-, respectively. The AdNDP analyses reveal that the C atom in Ge₄C forms one 4c-2e σ bond, two 4c-2e π bonds, and one 5c-2e σ bond with Ge atoms. The C atom in Ge₄C interacts with an H^- forming a C-H σ bond in Ge₄CH^-. AIMD simulation results indicate high dynamic stabilities of Ge₄C and Ge₄CH^- at 300 and 500 K. Our results show that the structures and chemical bonding of Ge₄B^- and Ge₄N⁺ are similar to those of Ge₄C, while those of Ge₄BH^2- and Ge₄NH resemble those of Ge₄CH^-.