Desorption and ablation regimes in UV-MALDI: the critical fluence

Although MALDI is a widely used technique, there is so far no theoretical description able to reproduce some critical aspects of the experimental results. For example, there is experimental as well as theoretical controversy regarding the minimum laser fluence, i.e., the so-called fluence threshold (F(T)), required to evaporate a sample. Furthermore, although the different processes involved in ion production have been the focus of many investigations, the fact is that the primary process for ion formation in MALDI is not desorption but ablation. In this work, we present a new phenomenological approach for understanding MALDI results based on a simple, but physically intuitive, idea consisting of limiting the laser–matter interaction process to three layers. This description allows us to consider the different processes that dominate ion formation, i.e., heat dissipation, as well as the different existing regimes. Concretely, we present the results for three different matrices, i.e., DHB, ferulic acid (FA) and α-cyano-4-hydroxycinnamic acid (CHCA), in the limit of low fluence. The simulations we carried out show great qualitative and pseudo-quantitative agreement with the experimental results. Also, based on the simulation results, it is possible to distinguish clearly between the two dominant regimes, i.e., desorption and ablation, and it is possible, therefore, to estimate the critical fluence (F(C)) that defines the transition from one regime to another.