Geometrical Structures and Dissociation Channels of CuP ( = 2-11): Studied by Mass Spectrometry and Theoretical Calculations.

Transition metal phosphorus cluster cations CuP (2 ≤ ≤ 11) were studied by laser ablation mass spectrometry and collision-induced dissociation (CID). The magic-numbered cluster ion of CuP was identified experimentally, and cluster ions of CuP and CuP were also found to be generated with high abundance. CID results show that the dissociation channels of CuP ( = 4 and 6-10) are all characterized by the loss of the P unit. Theoretical calculations combining global minima searching with the basin-hopping method and density functional theory (DFT) optimizations were performed for these clusters. Among them, the magic-numbered cluster CuP was characterized by a D symmetry, with the Cu atom bridging two P units. The most stable isomer of CuP was found to be characterized by a C symmetry. Calculations also reflect that the dissociation channels of the loss of the P unit are more energetically favorable than those of the loss of the P unit for CuP ( = 4 and 6-10), which are in good consistent with the experimental results.