Broadband Phase Correction of FT-ICR Mass Spectra via Simultaneous Excitation and Detection

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Abstract
In typical Fourier transform ion cyclotron resonance (FT-ICR) mass spectra, temporally dispersed excitation and the delay between excitation and detection result in continuous variation of signal phase with frequency in the detected time-domain ion signal. The complex frequency-domain spectrum of such a signal is a linear combination of absorption- and dispersion-mode spectral components with corresponding asymmetric peaks. For this reason, magnitude-mode spectral display is usually employed to yield a phase-independent uniform and symmetrical peak shape at the expense of spectral resolution. In this work, we implement simultaneous excitation and detection to enable Fourier deconvolution to recover absorption-mode spectra for both low- and high-field FT-ICR instruments. These spectra yield resolving power improvement factors approaching the maximum theoretical limit of 2.0, as well as reduction in frequency assignment errors relative to conventional magnitude-mode spectra. The Fourier deconvolution procedure has the additional benefit of correcting for spectral variation resulting from nonuniform power distribution over the excitation bandwidth and the potential benefit of providing useful diagnostic information for interpretation of experimental performance.

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