Kinetics and equilibrium of small metallic clusters: Ab initio confinement molecular dynamics study of 4

The ab initio molecular dynamics (AIMD) 1] is combined with the heuristic, successive confinement method of surveying a potential energy surface (PES) 2], thereby offering a framework for the simulation study of kinetics and equilibrium properties of metallic clusters. This approach is applied to the study of Au₄, a cluster possessing a simple but specific PES, which consists of very shallow and deep basins and due to this presents a challenge to the conventional AIMD methods. Among other things, the probabilities of the transitions between isomers have been found, and on this basis, both the time-dependent and equilibrium populations of the isomers have been calculated for the conditions typical of the NeNePo experiments 3] in the femtosecond pump-probe spectroscopy.