Geometrical Structures and Dissociation Channels of CuP2n + (n = 2-11): Studied by Mass Spectrometry and Theoretical Calculations.

Abstract

Transition metal phosphorus cluster cations CuP2n+ (2 ≤ n ≤ 11) were studied by laser ablation mass spectrometry and collision-induced dissociation (CID). The magic-numbered cluster ion of CuP8+ was identified experimentally, and cluster ions of CuP14+ and CuP18+ were also found to be generated with high abundance. CID results show that the dissociation channels of CuP2n+ (n = 4 and 6–10) are all characterized by the loss of the P4 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 CuP8+ was characterized by a D2d symmetry, with the Cu atom bridging two P4 units. The most stable isomer of CuP14+ was found to be characterized by a C2v symmetry. Calculations also reflect that the dissociation channels of the loss of the P4 unit are more energetically favorable than those of the loss of the P2 unit for CuP2n+ (n = 4 and 6–10), which are in good consistent with the experimental results.