Structure, dynamics and thermodynamics of small particles and inorganic clusters

Abstract

This invited review attempts to draw together recent advances in the structural characterisation of clusters and our theoretical understanding of dynamics, especially coexistence phenomena. It is now possible to characterise the potential energy surface of a small cluster in great detail, both in terms of local minima and transition states. A selection of results is collected includingab initio calculations on main group ligated clusters and a wide variety of systems bound by model analytic potentials. Useful comparisons may be made between the rearrangement mechanisms supported by the various potential energy surfaces. Furthermore, knowledge of transition states enables us to explain the results of dynamical simulations in great detail, and make comparisons with thermodynamic models. For larger systems, however, the number of stationary points is daunting, yet progress is still possible in terms of the underlying potential energy surface using the harmonic superposition approximation.