Multiple-ion-ejection multi-reflection time-of-flight mass spectrometry for single-reference mass measurements with...

Repeated switching of electric potentials within a single experimental cycle is introduced for a multi-reflection time-of-flight mass spectrometer (also known as an electrostatic ion beam trap) in order to eject different ion species after different storage times. The method is demonstrated with two cluster ions with considerably different mass-to-charge ratios (the A = 624 and 832 isotopologues of Pb₃ ⁺ and Pb₄ ⁺, respectively) for the specific case where the sequential ejections result in an identical number of revolution periods. Thus, the ions' flight lengths are identical, and the resulting time-of-flight values allow single-reference mass determination. The requirements for the switching time window are studied in detail. For the present system and ion pair, the relative mass uncertainty is found to be 3 · 10^-7 for short measurements (≈10 min) and 6 · 10^-8 for longer ones (≈2 h).