Modelling of multifrequency IRMPD for laser isotope separation

The process of infrared multiple photon dissociation (IRMPD) of molecules is of great fundamental importance and has practical significance, such as isotope separation etc. Unfortunately, a clear insight into the process has been hindered by the bewildering array of important variables affecting MPD. The dissociation probability g (phi) i.e. the yield has been found to be a sensitive function of laser fluence phi along with numerous other parameters like laser frequency, gas pressure etc. We have shown that in single frequency IRMPD, an accurate quantitative characterization of the dissociation probability can be adequately expressed by a ‘power law’ model with two fitting parameters namely critical fluence, phic and multiphoton order, m. This model was exploited in analysing our MPD results on various systems. However, the small isotope shift encountered in heavy elements and the sticking phenomenon observed in small light molecules restrict respectively the separation factor and the dissociation yield. These problems can effectively be tackled by irradiation with multifrequency laser beams which can be chosen appropriately on the basis of spectroscopic features. Based on our success in single frequency model, multifrequency IRMPD is modelled by a functional form containing the product of power law terms for individual fluences on irradiation frequencies. This model is successfully benchmarked with our experimental results on multifrequency LIS of tritium. Such knowledge can be utilized for appropriate separation process design, evaluation and optimization.