Tailored ion radius distribution for increased dynamic range in FT-ICR mass analysis of complex mixtures

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) typically utilizes an m/z-independent excitation magnitude to excite all ions to the same cyclotron radius, so that the detected signal magnitude is directly proportional to the relative ion abundance. However, deleterious space charge interaction between ion clouds is maximized for clouds of equal radius. To minimize ion cloud interactions, we induce an m/z-dependent ion radius distribution (30%-45% of the maximum cell radius) that results in a 3-fold increase in mass spectral dynamic range for complex mixtures, consistent with increased ion cloud lifetime for less-abundant ion clouds. Further, broadband frequency-sweep (chirp) excitation that contains the second and/or third harmonic frequency of an excited ion cloud swept from low-to-high frequency produces systematic variations in accurate mass measurement not observed when the sweep direction is reversed. The ion cyclotron radius distribution induces an m/z-dependent frequency shift that can be corrected to provide a root-mean-square (rms) mass measurement error of <100 ppb on petroleum-based mixtures that contain tens of thousands of identified peaks.