Since time-of-flight mass spectrometers were first introduced, there has been the need to improve mass resolution, which depends largely upon the initial conditions of the ions at the time they are formed. For larger ions, metastable fragmentation presents an even more serious challenge, although such processes may be utilized to obtain product ion mass spectra in instruments equipped with a reflecting field. Initial conditions and internal energy are all determined during the ionization process, so that ion extraction, focusing, detection, recording and other aspects of time-of-flight analyzer design must be suited to the ionization method used. Thus, this chapter presents the basic principles governing time-of -flight mass measurement and resolution, describes the role of reflectrons and other energy focusing devices, and reviews several unique time-of -flight configurations that have been, or are currently being, used.An attractive feature of the time-of-flight mass spectrometer is its simple design (Figure la). Ions are formed in a short source region (s), defined generally by a backing plate and an extraction grid. A positive voltage (V) placed on the backing plate imposes an electric field (E = V/s) across the source region, which accelerates all of the ions to the same kinetic energy:where m = the mass of the ion, ν = its velocity, e = the charge on an electron, and ζ = number of charges. As the ions pass through the extraction grid they will have velocities which depend inversely upon the square root of their mass: 1/2 [2] IzeEs m 0097-6156/94/0549-0016$09.25/0