PNNL

Abstract

Field Asymmetric waveform Ion Mobility Spectrometry (FAIMS) has significant potential for post-ionization separations in conjunction with MS analyses. FAIMS exploits the fact that ion mobilities in gases depend on the electric field in a manner specific to each ion, which allows one to fractionate ion mixtures. Nearly all previous work has used pure gases, for which FAIMS fundamentals are understood reasonably well. However, experiments in gas mixtures like N2/CO2 have uncovered unexpected phenomena that remained unexplained. Here we introduce a universal model for FAIMS separations in mixtures, derived from the formalisms that determine high-field mobilities in heteromolecular gases. Overall, the theoretical findings are consistent with the data in N2/CO2, though quantitative discrepancies remain. As a control, modeled results for N2/O2 fit Blanc’s law, in agreement with measurements. Calculations for He/N2 are broadly consistent with observations, and show why adding He to the working gas enhances FAIMS performance. We predict spectacular non-Blanc effects in mixtures of extremely disparate gases such as He/CO2, which could improve the peak capacity and sensitivity of technique. Understanding the FAIMS operation in gas mixtures will enable rational design of media for both targeted and global analyses.