Limitation of time-of-flight resolution in the ultra high mass range

In this work, we have examined the reason for the deterioration of resolution and mass accuracy of time-of-flight mass analyzers with increasing mass after the expansion-induced kinetic energy has been eliminated by collisional cooling in an ion guide. Theoretically, removing the expansion-induced kinetic energy by collisional cooling permits the ions to travel along the ion guide axes without significant deviation so that they can be injected into the analyzer in a well-collimated ion beam with well-defined kinetic energy. If the ions can be injected into an orthogonal acceleration time-of-flight mass analyzer (oa-TOF) in this manner, high-resolution mass analysis can be obtained regardless of mass or m/z. Unfortunately, high resolution did not result. It is our contention that the effusive expansion out of the first ion guide yields dispersive axial ejection that reduces TOF resolving power with increasing mass not m/z.