Electron-ion-ion coincidence experiments for photofragmentation of polyatomic molecules using pulsed electric fields: Treatment of random coincidences

In molecular photofragmentation processes by soft X-rays, a number of ionic fragments can be produced, each having a different abundance and correlation with the kinetic energy of the emitted electron. For investigating these fragmentation processes, electron-ion and electron-ion-ion coincidence experiments, in which the kinetic energy of electrons are analyzed using an electrostatic analyzer while the mass of the ions is analyzed using a pulsed electric field, are very powerful. For such measurements, however, the contribution of random coincidences is substantial and affects the data in a non-trivial way. Simple intuitive subtraction methods cannot be applied. In the present paper, we describe these electron-ion and electron-ion-ion coincidence experiments together with a subtraction method for the contribution from random coincidences. We provide a comprehensive set of equations for the data treatment, including equations for the calculation of error-bars. We demonstrate the method by applying it to the fragmentation of free CF₃ SF₅ molecules.