Simulation of Space Charge Effects in Fourier Transform Quadrupole Ion Traps (FT-QITs).

We present ion dynamics simulations regarding the effect of space charge on the performance of Fourier transform quadrupole ion traps (FT-QITs) with special attention to signal stability, mass resolving power, and sensitivity. Ion trajectory simulations within an idealized QIT geometry are performed by applying a dedicated application (QITSim) using an in-house developed open simulation framework (IDSimF). Image current detection transients are generated by the application and are subsequently transformed into frequency spectra of ion secular motion. Such frequency spectra are the basis for the calculation of mass spectra in FT-QIT instruments. The simulation results are used to assess the extent of space charge induced effects regarding the analytical performance of FT-QIT systems. The simulation results for two Cl⁺ and seven Xe⁺ isotope ions exhibit diverse space charge induced phenomena. Most prominently, complete isotope signal fusion, quantitative individual signal suppression, and severe signal distortions are observed even at low absolute numbers of trapped ions. Furthermore, significant shifts of the secular oscillation frequencies occur, even when the signal shape appears to be mostly unaffected and when the frequency separation for trapped ions with different masses is large. This significantly limits the applicability of FT-QIT systems for high resolution mass spectrometry. An increase of the RF amplitude of the trapping field as well as increasing the extent of ion excitation partly mitigate these adverse space charge effects; nevertheless, the usable operational range of the simulated FT-QIT system for analytical applications remains rather narrow.