Photoionization

Photoionization is the physical process in which an ion is formed from the interaction of a photon with an atom or molecule. Not every interaction between a photon and an atom, or molecule, will result in photoionization. The probability of photoionization is related to the photoionization cross section of the species – the probability of an ionization event conceptualized as a hypothetical cross-sectional area. This cross section depends on the energy of the photon (proportional to its wavenumber) and the species being considered i.e. it depends on the structure of the molecular species. In the case of molecules, the photoionization cross-section can be estimated by examination of Franck-Condon factors between a ground-state molecule and the target ion. This can be initialized by computing the vibrations of a molecule and associated cation (post ionization) using quantum chemical software e.g. QChem. For photon energies below the ionization threshold, the photoionization cross-section is near zero. But with the development of pulsed lasers it has become possible to create extremely intense, coherent light where multi-photon ionization may occur via sequences of excitations and relaxations. At even higher intensities (around 1015 – 1016 W/cm2 of infrared or visible light), non-perturbative phenomena such as barrier suppression ionization and rescattering ionization are observed. Several photons of energy below the ionization threshold may actually combine their energies to ionize an atom. This probability decreases rapidly with the number of photons required, but the development of very intense, pulsed lasers still makes it possible. In the perturbative regime (below about 1014 W/cm2 at optical frequencies), the probability of absorbing N photons depends on the laser-light intensity I as IN . For higher intensities, this dependence becomes invalid due to the then occurring AC Stark effect. Resonance-enhanced multiphoton ionization (REMPI) is a technique applied to the spectroscopy of atoms and small molecules in which a tunable laser can be used to access an excited intermediate state.