Matrix methods for the calculation of stability diagrams in quadrupole mass spectrometry

The theory of the computer calculation of the stability of ion motion in periodic quadrupole fields is considered. A matrix approach for the numerical solution of the Hill equation and examples of calculations of stability diagrams are described. The advantage of this method is that it can be used for any periodic waveform. The stability diagrams with periodic rectangular waveform voltages are calculated with this approach. Calculations of the conventional stability diagram of the 3-D ion trap and the first six regions of stability of a mass filter with this method are presented. The stability of the ion motion for the case of a trapping voltage with two or more frequencies is also discussed. It is shown that quadrupole excitation with the rational angular frequency omega = NOmega/P (where N, P are integers and Omega is the angular frequency of the trapping field) leads to splitting of the stability diagram along iso-P lines. Each stable region of the unperturbed diagram splits into P stable bands. The widths of the unstable resonance lines depend on the amplitude of the auxiliary voltage and the frequency. With a low auxiliary frequency splitting of the stability diagram is greater near the boundaries of the unperturbed diagram. It is also shown that amplitude modulation of the trapping RF voltage by an auxiliary signal is equivalent to quadrupole excitation with three frequencies. The effect of modulation by a rational frequency is similar to the case of quadrupole excitation, although splitting of the stability diagram differs to some extent. The methods and results of these calculations will be useful for studies of higher stability regions, resonant excitation, and non-sinusoidal trapping voltages. (J Am Soc Mass Spectrom 2002, 13, 597-613) (C) 2002 American Society for Mass Spectrometry.