On the high‐resolution mass analysis of the product ions in tandem time‐of‐flight (TOF/TOF) mass spectrometers using a time‐dependent re‐acceleration technique

The time‐dependent reacceleration of product ions produced as a result of dissociation of a single precursor ion in a tandem time‐of‐flight mass spectrometer is considered for the first time. Analytical expressions for the shapes of electric pulses bringing all the kinetic energies of the product ions to the same value are derived for two cases: forward acceleration mode and deceleration, followed by re‐acceleration in the reversed direction (reversed mode). Secondary time‐of‐flight focusing resulting from the re‐acceleration in the reversed mode is shown to be mass‐dependent and, when averaged over a wide mass range, the focusing is tight enough to provide mass resolution exceeding 10 000. After time‐dependent re‐acceleration, additional compression of the ion packet width leading to better mass resolution can be obtained by decelerating the ions in a constant field. Copyright © 2009 John Wiley & Sons, Ltd.