Phosphoranide production and decomposition in the gas phase.

After characterizing the negative ion chemistry of tris(trifluoromethyl) phosphine in a previous work, new insights about the interpretation of the MS/MS mass spectrum of the phosphide anion (CF3)2P- m/z 169 could be revealed and are described in this current work. The phosphide (CF3)2P- anion, m/z 169, was accelerated in a cloud of (CF3)3P neutrals and new product ions could be detected which do not belong to fragmentation channels. Instead, high mass anions m/z 207 and m/z 257 are found, and the reaction mechanism could be revealed by density functional theory (DFT) calculations at B3LYP/6-311 + G(3df)//B3LYP/6-31 + G(2d) level of theory. The formation of the phosphoranide (CF3)3PF- m/z 257 is the result of a fluoride anion transfer from the accelerated phosphide anion (CF3) 2P- m/z 169 to the (CF3)3P neutral m = 238. Decomposition of the newly formed phosphoranide (CF3) 3PF- m/z 257 leads to the formation of smaller phosphoranides (CF3)2PF2 - m/z 207 and CF3PF3 - m/z 157 as a result of successive CF2 eliminations. A new rearrangement in the formed phosphoranide (CF3)2PF2 - could be revealed, whereby a CC bond formation can take place and the product anion C 2F5 - m/z 119 could be experimentally obtained

Prefocusing inside a linear ion beam guide - a SIMION study.

A set of 14 stacked ring electrodes was studied by the SIMION ion trajectory simulation program under a pressure of 1 Pa with different applied RF frequencies and RF voltage amplitudes when a classical DC gradient of 38 V/cm is applied. Ion–neutral collision effects were considered by adopting a successful and integrated hard sphere, elastic, ion–neutral collision user program provided by SIMION. Mass dependent ion transmission efficiencies could be obtained. In the classical operation mode of the ion beam guide, a RF frequency of 2 MHz was crucial to obtain very good ion transmission efficiency along a broad mass range. Lower RF frequencies (<1.5 MHz) limited the good transmission efficiencies only to high masses with m/z > 500 amu. SIMION can reproduce expected efficiency curves which show that low m/z ions below 150 amu represent a challenge for such linear ion beam devices even when high RF driving frequency of 2 MHz is applied. The simulations also show that a DC gradient of at least 30 V/cm is crucial to maintain good transmission efficiencies which are in agreement with previously published results. A new operation mode for running the same device is introduced for earlier ion focusing in between the second and fifth ring electrodes, prior to slight beam divergence after the focus point. This required a significant change of the applied DC voltages to alter the shape of the DC gradient curve along the central z axis. The newly identified operation mode allows enhancing the mass dependent ion transmission efficiency in a wide m/z range between 80 and 1000 amu when an RF frequency of 2 MHz is applied to the first ten ring electrodes