Solvents have a profound influence on chemical reactions in solution and have long been used to control their outcome. Such effects are generally considered to be governed by thermodynamics; however, little is known about the steric effects of solvent molecules. Here, we probe the influence of individual solvent molecules on reaction dynamics and present results on the atomistic dynamics of a microsolvated chemical reaction--the fundamentally important nucleophilic substitution reaction. We study the reaction of OH(-) with CH(3)I using a technique that combines crossed-beam imaging with a cold source of microsolvated reactants. Our results reveal several distinct reaction mechanisms for different degrees of solvation; surprisingly, the classical co-linear substitution mechanism only dominates the dynamics for mono-solvated reactants. We analyse the relative importance of the different mechanisms using ab initio calculations and show that the steric characteristics are at least as relevant as the energetics in understanding the influence of solvent molecules in such microsolvated reactions.

We study experimentally and theoretically structural defects which are formed during the transition from a laser cooled cloud to a Coulomb crystal, consisting of tens of ions in a linear radio frequency trap. We demonstrate the creation of predicted topological defects ("kinks") in purely two-dimensional crystals and also find kinks which show novel dynamical features in a regime of parameters not considered before. The kinks are always observed at the center of the trap, showing a large nonlinear localized excitation, and the probability of their occurrence saturates at ∼0.5. Simulations reveal a strong anharmonicity of the kink's internal mode of vibration, due to the kink's extension into three dimensions. As a consequence, the periodic Peierls-Nabarro potential experienced by a discrete kink becomes a globally confining potential, capable of trapping one cooled defect at the center of the crystal.

We present a study of the different product channels in the reactions of OH and OH-(H2O) with methyl iodide over a range of collision energies. Direct dynamics classical trajectory simulations are employed to obtain an atomistic comparison with the experimental results. For the experiments we have combined a crossed beam ion imaging setup with a multipole rf ion trap. The trap allows us to prepare the molecular and cluster ions with a controlled internal temperature and thus provides well-defined initial conditions for reaction experiments at low collision energy. Changing the internal temperature of the cluster ions was found to have a profound effect on their reactivity.

We study discrete solitons (kinks) accessible in the state-of-theart trapped ion experiments, considering zigzag crystals and quasi-threedimensional configurations, both theoretically and experimentally. We first extend the theoretical understanding of different phenomena predicted and recently experimentally observed in the structure and dynamics of these topological excitations. Employing tools from topological degree theory, we analyze bifurcations of crystal configurations in dependence on the trapping parameters, and investigate the formation of kink configurations and the transformations of kinks between different structures. This allows us to accurately define and calculate the effective potential experienced by solitons within the Wigner crystal, and study how this (so-called Peierls-Nabarro) potential gets modified to a non-periodic globally trapping potential in certain parameter regimes. The kinks' rest mass (energy) and spectrum of modes are computed and the dynamics of linear and nonlinear kink oscillations are analyzed. We also present novel, experimentally observed, configurations of kinks incorporating a large-mass defect realized by an embedded molecular ion, and of pairs of interacting kinks stable for long times, offering the perspective for exploring and exploiting complex collective nonlinear excitations, controllable on the quantum level.