Grant: Discovery Grants Program - Individual

With the recent advances in (ultrafast) spectroscopy, which now permit the observation of molecular systems in great detail and chemical reactions in real time, there is an ever increasing interest in theoretical studies of chemical reaction dynamics and thermodynamics, as they can predict, explain and guide experiments. In particular, molecular dynamics techniques allow the motion of atoms and molecules to be simulated at the microscopic level, providing invaluable information about the mechanism and kinetics of chemical reactions. These studies are essential since they provide a link between potential energy surfaces calculated by electronic structure theory (quantum chemistry) and experimental measurements of chemical dynamics and thermodynamics. In many instances, experimental observables are too convoluted to explain and understand without the help of theory. Furthermore, connection with experiment is crucial for assessing the reliability of computer simulations and theoretical models, which, in turn can be used to improve our fundamental understanding of chemistry.New directions are proposed for the development of tools aimed at realistic computer simulations, which include an improved description of molecular interactions and the inclusion of quantum nuclear effects and possible nonadiabatic effects in dynamical simulations. Most applications will focus on clusters, which are aggregates of atoms or molecules which bridge the gap between the gas and condensed (liquid) phases. Clusters can be used as tools for selective microsolvation, or they can be a distinct class of materials with unique properties. We will study, in particular, (1) the structure and reactions of cluster nanomaterials, (2) the photochemistry of solvent clusters seeded by ions and salts, and (3) the cluster and bulk solvation of complex ions and salts. Our theoretical studies will help explain and guide experimental studies, and will contribute to a deeper molecular-level understanding of chemistry, with diverse potential applications from nanotechnology (e.g. hydrogen/energy storage, catalysis) to biology (e.g. protein denaturation).