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

[Image: see text] Transition metal phosphorus cluster cations CuP(2n)(+) (2 ≤ n ≤ 11) were studied by laser ablation mass spectrometry and collision-induced dissociation (CID). The magic-numbered cluster ion of CuP(8)(+) was identified experimentally, and cluster ions of CuP(14)(+) and CuP(18)(+) were also found to be generated with high abundance. CID results show that the dissociation channels of CuP(2n)(+) (n = 4 and 6–10) are all characterized by the loss of the P(4) 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(8)(+) was characterized by a D(2d) symmetry, with the Cu atom bridging two P(4) units. The most stable isomer of CuP(14)(+) was found to be characterized by a C(2v) symmetry. Calculations also reflect that the dissociation channels of the loss of the P(4) unit are more energetically favorable than those of the loss of the P(2) unit for CuP(2n)(+) (n = 4 and 6–10), which are in good consistent with the experimental results.