Cluster properties in the regime in which each atom counts

In this contribution we address (A) size selective reactivity of anionic gold clusters relevant for catalysis and (B) femtochemistry of metallic clusters and its control by tailored laser fields. In this connection the following results will be presented. (I) General mechanism for co-adsorption of O2 and CO based on structure–reactivity relation has been obtained using DFT method which permits to elucidate fully available experimental results. (II) Simulation of pump–probe signals in the framework of negative-to-neutral-to-positive (NeNePo) spectroscopy using combination of Wigner distribution approach and MD “on the fly” allows to determine experimental conditions under which different processes such as geometric relaxation and internal vibrational relaxation (IVR) in Ag2Au can be observed. (III) We show that optimal control theory can be used as a tool for analysis of ultrafast processes on example of photoionization processes in NaK, since the shapes of the optimized pulses based on full quantum mechanical treatment can be used to deduce the mechanisms of the processes underlying the optimal control.