ToF‐SIMS and computation analysis: Fragmentation mechanisms of polystyrene, polystyrene‐d 5 , and polypentafluorostyrene

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EarlyView Article

  • Published: Dec 19, 2017
  • Author: Kai‐Mo Ng, Yiu‐Ting R. Lau, Lu‐Tao Weng, King‐Lun Yeung, Chi‐Ming Chan
  • Journal: Surface and Interface Analysis

We studied the time‐of‐flight secondary ion mass spectrometry fragmentation mechanisms of polystyrenes—phenyl‐fluorinated polystyrene (5FPS), phenyl‐deuterated polystyrene (5DPS), and hydrogenated polystyrene (PS). From the positive ion spectra of 5FPS, we identified some characteristic molecular ion structures with isomeric geometries such as benzylic, benzocyclobutene, benzocyclopentene, cyclopentane, and tropylium systems. These structures were evaluated by the B3LYP‐D/jun‐cc‐pVDZ computation method. The intensities of the C7H2F5+ (m/z = 181), CyPent‐C9H3F4+ (m/z = 187), CyPent‐C9H4F5+ (m/z = 207), and CyPent‐C9H2F5+ (m/z = 205) ions were enhanced by resonance stabilization. The positive fluorinated ions from 5FPS tended to rearrange and produce fewer fluorine‐containing molecular ions through the loss of F (m/z = 19), CF (m/z = 31), and CF2 (m/z = 50) ion fragments. Consequently, the fluorine‐containing polycyclic aromatic ions had much lower intensities than their hydrocarbon counterparts. We propose the fragmentation mechanisms for the formation of C5H5+, C6H5+, and C7H7+ ion fragments, substantiated with detailed analyses of the negative ion spectra. These ions were created through elimination of a pentafluoro‐phenyl anion (C6F5) and H+, followed by a 1‐electron‐transfer process and then cyclization of the newly generated polyene with carbon‐carbon bond formation. The pendant groups with elements of different electronegativities exerted strong influences on the intensities and fragmentation processes of their corresponding ions.

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