Applications of molecular Rydberg states in chemical dynamics and spectroscopy

Molecules in high Rydberg states, in which one electron has been excited into a hydrogenic orbital of large mean radius, have many unusual properties compared to ground state molecules. These properties, which are reviewed in this article, make them suitable for a diverse and growing number of applications in chemical dynamics. The most recent methods for studying molecular Rydberg states using high-resolution spectroscopy and theory, including effects of electric fields, are described here. An important feature is the high susceptibility of Rydberg states to external field perturbation which not only has a profound effect on the observable energy levels, spectroscopic intensities and lifetimes, but is also useful for state-selective detection through field ionization. The large dipole moment that can be created in a field is also useful for controlling the motion of molecules in Rydberg states. The applications reviewed here include: ZEKE (zero kinetic energy), MATI (mass-analyzed threshold ionization) and PIRI (photo-induced Rydberg ionization) spectroscopy; pulsed-field recombination of ions and electrons; the state selection and reaction of molecular ions; collisions of Rydberg states with neutrals, ions and metallic surfaces; Rydberg tagging and imaging of products of photodissociation; and the control of translational motion and orientation via the use of inhomogeneous fields.