Laser ablation synthesis of new phosphorus nitride clusters from α-P3N5 via laser desorption ionization and matrix assisted laser desorption ionization time-of-flight mass spectrometry

Phosphorus nitride clusters generated during Laser Desorption Ionization (LDI) and Matrix‐Assisted Laser Desorption Ionization (MALDI) of solid P3N5 were analyzed via Time‐of‐Flight Mass Spectrometry (TOF MS). The LDI TOF mass spectra show the formation of series of clusters: PmNn+ {(m = 1; n = 8–11), (m = 4; n = 3–4), (m = 5; n = 1–5), (m = 6; n = 1–3, 5–8), (m = 2–7; n = 1), (m = 5–10; n = 2), (m = 4–6; n = 3), (m = 4,5; n = 4), (m = 5,6; n = 5)}, and PmNn– (m = 4,5; n = 1). Using 3‐hydroxypicolinic acid (HPA) as a matrix the PmNn+ species (m = 1–4, 6, 8) with a high nitrogen content (n = 4, 5, 8, 10–12, 20) were identified. The formation of a N6– cluster was also detected using a C60 matrix. Under various conditions singly charged Pm+ (m = 2–7, 9, 13), Pm– (m = 3–11, 13, 15, 17), Nn+ (n = 5, 9, 10, 12, 13), and Nn– (n = 6, 10‐15) clusters were identified in the mass spectra. Such high nitrogen content clusters (up to N15–) generated by laser desorption from a solid material are described for the first time. The stoichiometry of the PmNn clusters was determined via isotopic envelope analysis and computer modelling. The composition of the clusters with respect to the crystalline structure of α‐P3N5 is discussed. Copyright © 2011 John Wiley & Sons, Ltd.