Abstract
Secular frequency scanning is a method of mass selectively scanning ions out of a quadrupole ion trap by linearly ramping the frequency of the resonance ejection signal through ion secular frequencies at constant rf amplitude and frequency. The method is electronically much simpler than resonance ejection but it requires a complex nonlinear calibration procedure to correlate mass-to-charge with time. A method of secular frequency scanning in quadrupole ion traps is described in which mass-to-charge is linear with time. This method, termed an "inverse Mathieu q scan", contrasts with linear frequency sweeping which requires a complex nonlinear mass calibration procedure. In the current method, mass scans are forced to be linear with time by scanning the frequency of the supplementary ac so that there is an inverse relationship between the ejected ion's Mathieu q parameter and time. In all cases, excellent mass spectral linearity is observed. The rf amplitude is shown to control both the scan range and the scan rate, whereas the ac amplitude and scan rate influence the mass resolution. The scan rate depends linearly on the rf amplitude, a unique feature of this scan. Although changes in either rf or ac amplitude affect the positions of peaks in time, they do not change the mass calibration procedure since this only requires a simple linear fit of m/z vs time. Space charge effects are shown to give rise to significant changes in resolution as well as to mass shifts. A method of secular frequency scanning which provides a linear mass scale has been demonstrated. The inverse Mathieu q scan offers a significant increase in mass range and power savings while maintaining access to linearity, paving the way for a mass spectrometer based completely on ac waveforms for ion isolation, ion activation, and ion ejection. Copyright © 2016 John Wiley & Sons, Ltd.
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