Interpretation and Simulation of Negative Ion Mass Spectra of Some Phosphorus Organoelement Compounds

Negative ion mass spectra for a series of organophosphorus compounds were obtained and negative ion fragmentation processes were treated theoretically. Using O-isopropyl and O-pinacolyl methylphosphonofluoridates as examples, electron affinities of molecules and their fragments were estimated using the UB3LYP/6-311+G(d,p) quantum-chemical approach and energetically more favorable and characteristic routes of dissociative electron attachment, including simple bond cleavage and rearrangements, were determined. Based on the obtained experimental and theoretical data, hypothetic fragmentation patterns were proposed and a special algorithm was compiled to predict negative ion mass spectra for some groups of organophosphorus compounds, such as D-alkyl methylphosphonofluoridates, D,D-alkyl phosphonodichloridates, and D,D'-dialkyl phosphonochloridates. The simulated mass spectra showed a good agreement with the experimental ones, confirming reasonable reliability of the proposed algorithm.