Medium‐sized phosphorus cluster cations P⁺_2m+1 (6 ≤ m ≤ 32) studied by collision‐induced dissociation mass spectrometry

Abstract

Medium-sized phosphorus cluster cations were generated by laser ablation of red phosphorus and investigated by the method of collision-induced dissociation mass spectrometry. Experimental results show that the primary dissociation channels of phosphorus cluster cations of P(+) 2m+1 (6 ≤ m ≤ 11) are all characterized by the loss of P4 unit. For larger cluster cations, their dissociation pathways were more complex. For those magic cations of P(+) 8k+1 observed previously, their dissociation pathways progressively change from the loss of P4 unit (for k = 3) to the loss of P8 unit (for k = 4, 5). A new dissociation pathway characterized by the loss of P10 unit was also indentified for larger cations of P(+) 8k+1 (6 ≤ k ≤ 8). Theoretical calculation also shows that, for cations of P(+) 2m+1 (4 ≤ m ≤ 10), the dissociation channel characterized by the loss of P4 unit is more energetically favorable than other dissociation channels, which is in good agreement with the experimental results.

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

“…Both spectra are quite similar in the distributions of the identified species. Besides the strong signals of P 2 n + 1 + (5 ≤ n ≤ 12) that have been previously observed in the laser ablation mass spectrum of red phosphorus, , new cluster ions of CuP 2 n + ( n = 4–10), Cu 2 ClP 2 n + ( n = 4–8), and Cu 3 Cl 2 P 2 n + ( n = 2, 4, 5, and 7) were clearly identified in both spectra. For the observed species of CuP 2 n + in both cases, the ion of CuP 8 + has much higher intensities than its adjacent ions and thus can be considered as a magic-numbered cluster.…”

“…The results are quite similar to the previously reported CID results of phosphorus cluster cations of P 2 m + ( m = 6–11) but are different from those of P 2 m – . 18 , 19 …”

“…Our previous studies on phosphorus clusters show that the method of B3LYP/6-311+G(d) can provide quite reasonable results. 18 , 19 , 23 Thus, the top 10 isomers for each cluster were picked out and finally optimized at this level. These structures were further verified by vibrational frequency analysis.…”

Detecting Dissociation Dynamics of Phosphorus Molecular Ions by Atom Probe Tomography

“…This can be ascribed to the structure of phosphorus cations assembled on the tip surface. In fact, the formation of P 2 , P 3 , and in particular P 4 subunits is energetically more favorable than larger phosphorus cations. − This is confirmed by atom probe data, where P 3 + and P 4 + ions appear as the most abundant species in the mass spectrum (Figure ). Similar conclusions were observed in collision-induced experiments performed by Huang et al in ref .…”

Search for Global Minimum Structures of P2n+1+ (n = 1–15) Using xTB-Based Basin-Hopping Algorithm

“…Thus, a better understanding about phosphorus clusters can deepen our knowledge about its structures and properties. The second fact is that although phosphorus cluster ions with wide size distributions have been observed in the laser ablation experiments for a long time (Martin, 1986;Mu et al, 2015;Yang et al, 2016;Kong et al, 2019), its structural studies are still limited for small to medium-sized clusters (Guo et al, 2004;Xue et al, 2010;Mu et al, 2015;Kong et al, 2019). And searching for the global minima in their PES is still a challenging task due to the diverse bonding patterns of the element.…”