The large electric dipole moments associated with highly excited Rydberg states of atoms and molecules make gas-phase samples in these states very well suited to deceleration and trapping using inhomogeneous electric fields. The methods of Rydberg-Stark deceleration with which this can be achieved are reviewed here. Using these techniques, the longitudinal motion of beams of atoms and molecules moving at speeds as high as 2500 m/s have been manipulated, with changes in kinetic energy of up to |Δ E kin|=1.3×10−20 J (|Δ E kin|/e=80 meV or |Δ E kin|/h c=650 cm −1) achieved, while decelerated and trapped samples with number densities of 106– 107 cm −3 and translational temperatures of ∼150 mK have been prepared. Applications of these samples in areas of research at the interface between physics and physical chemistry are discussed.
This thesis describes contributions to the development of a new method to control the translational motion of atoms and molecules in supersonic beams.This method, Rydberg-Stark deceleration, is in principle applicable to all atoms and molecules in the gas phase.It relies on the Stark effect exhibited by Rydberg states and enables the production of samples of translationally and internally cold atoms and molecules which have possible applications in high-resolution spectroscopic experiments, in the studies of collisions at low temperatures and in quantum information science.This method has been developed and tested in deceleration and trapping experiments on hydrogen and deuterium atoms, and hydrogen molecules initially moving in supersonic beams.Its power originates from the large dipole moments, easily exceeding 1000 Debye, induced in Rydberg states by electric fields.Large forces are exerted on Rydberg atoms and molecules